Negi seems to get along well with mostly all of his students. Their feelings for him can vary from friendship to love though Negi is oblivious to anything other than friendly relationships. Most of his students like him to which their interests in Negi progresses throughout the story; most have sizable crushes on him, some see him as a younger brother, a few act as mother figures to him, a few have fallen in love with him, while others think of him as a close friend.
- Asuna Kagurazaka: Negi and Asuna's relationship starts off on very shaky ground, as he was forced to live in the same room with her as a request from the academy's dean, but also happened to replace the homeroom teacher she happened to have a crush on. However, their relationship quickly improves as they get used to each other. Curiously, Asuna resembles Nekane a lot, so it was easy for Negi to develop a little brother/big sister relationship with her. Asuna was the first to find out about Negi's secret and was the first person that Negi made a probationary contract with, when his life was threatened by Evangeline. Her strength, determination and immunity to enemy magic proved to be invaluable in many dangerous situations.
- Konoka Konoe: Negi's other roommate, and the dean's granddaughter. She always acts as a mediator between Asuna and Negi when there is tension between them. As the heir to the "Kansai Magic Association", a powerful group of mages from Western Japan, she was attacked by enemies who wanted to harness her latent magical power, but was protected by Negi and his allies. Since then, she studies magic under Negi and Evangeline, and even made a probationary contract with him, gaining great healing abilities along with basic magic.
- Setsuna Sakurazaki: One of Negi's closest students and allies. She is a hanyo, or half demon, who has sworn to protect Konoka Konoe, and is an expert at Shinmei-ryu (lit. God-Crying Style). Though at first she stated that she was disappointed at Negi's so far performance during the Kyoto Field Trip Arc, Setsuna soon realized that not only was he a valuable ally, but a great leader and teacher as well. She also makes a probationary contract with Negi during this arc to better increase their chances of defeating a horde of yokai summoned by Chigusa Amagasaki. As the series has progessed, her relationship with Negi has grown to the point where she would even state she would not stand by if Negi were threatened, and would protect his life as she would do for Konoka. She highly respects Negi as both a teacher and a friend.
- Evangeline A.K. McDowell: A former enemy of Negi, she is a powerful true vampire criminal who had most of her powers sealed by the thousand master 15 years ago, being trapped in Mahora Academy since then. Nagi promised to release her from this curse someday, but Eva's hopes for it to happen were crushed by the news of his disappearance. When Negi moved to the Academy, she tried to attack him in order to drain his blood to obtain enough power to break free by herself, until Negi defeated her with Asuna's help. Later in the series, Negi decides to ask her to instruct him in magic as her apprentice, occasionally giving her a bit of his blood as payment. Just like she was in love with Nagi (and some chapters showed she still does), she seems to be developing some feelings for Negi as well, though she is reluctant to admit it.
- Kū Fei: Just like Negi sought Eva's aid to increase his magical abilities, he now trains under Kū Fei in Chinese Kenpo, hoping to be strong enough in both magic and close combat just like his father. She also develops feelings for Negi as the story progresses, stating that one day he can become her husband. She later confesses her love to Negi and felt that he has gotten stronger than her, therefore causing her to fall in love with him. She eventually made a Pactio with Negi during the trip to the Magic World.
- Ayaka Yukihiro: 3-A's class representative. She is the girl most overtly fond of Negi, though she stands by the position that she is only interested in Negi because he "needs a mother figure" or a "big sister". Actually her feelings for him are a mixture of physical infatuation and brotherly love, as she apparently still has not gotten over the loss of her younger brother, who died during birth the same year Negi was born. She is currently helping out in Negi's plan. According to her, she admits that her current relationship with Negi can now even referred to as "partners", at least in her perspective.
- Nodoka Miyazaki: Soon after Negi became her teacher, she developed a crush on him despite her nervousness around guys. Always supported by her best friend Yue (who has now developed her own feelings for him), she is the first one of Negi's students to properly confess her love to him. She is also the first one to have a real (non Pactio related) kiss with Negi. She is the second student to form a provisional contract. Obtaining an item that can give her access to the thoughts of anyone, Nodoka became an invaluable asset in his party.
- Chao Lingshen: The main antagonist of the Mahora Festival arc, she gave some trouble to Negi and his friends during the festival, claiming that she came from the future and is in reality a descendant of Negi. She also claims her true intentions are to change the world for the better suggesting that something happens in her time that was bad enough to want to change history to stop it. She was defeated by Negi in the end. Before she returned to the future, Negi wanted her to stay with him as his "partner" which she quietly agrees to, however she decides otherwise due to Negi practically "confessing his love to her" and being his blood relative. Chao then leaves back to the future believing one day the two meet again.
- Chisame Hasegawa: Originally seeing Negi as a bizarre brat, Chisame has slowly warmed up to Negi. Her opinion of Negi starts to change when she learns he is a fan of her homepage on the web. Negi also helps Chisame come out of her introverted shell into a more confidant individual. In Asuna’s absence, she designates herself as temporary guardian of Negi. This doesn’t happen until later volumes in the manga when Negi fulfills a promise to her saving her from a tentacle monster. Currently, she is one of the few girls that has a platonic relationship with Negi and does not have romantic feelings for him, however she does show signs of "jealousy" toward the other girls who express affections towards Negi, making her possibly "one" of them.
- Chachamaru Karakuri: Originally as Evangeline's partner through a 'Doll Contract', she eventually develops feelings for Negi as the story progresses. During Kurt Godel's party, Chachamaru wonders about performing a Pactio with Negi, despite that she is a robot and does not have a soul. However, Negi never gives up in succeeding performing a Pactio with her, and then her Pactio card finally appears. According to Evangeline, she thinks no one other than Chachamaru who would help him in his plan. Chachamaru is currently still not able to confess properly to Negi yet, but her feelings for him is on the same level as Nodoka's and Makie's. She is also Negi's Secretary.
- Ako Izumi: She had no interest in Negi from the start, but she falls in love with 'Nagi' (which is Negi in his disguise) during the Mahora Festival arc. She later had a hard time being a slave in the Magical World alongside Akira and Natsumi. After overhearing Tosaka's conversation with 'Nagi' which he reveals that 'Nagi' is Negi, she became heartbroken. However, she gotten over it and tried to persuade Tosaka to forget about Negi's true identity to which he immediately agrees with no second thoughts. After that, Negi meets Ako as 'Nagi' tried to apologize to her, but she does not mind and she soon give him a kiss and confessed to him. When she meets Negi in his Demon form, she became terrified but after seeing Makie did not hesitate to calm him down, she became impressed and soon tried helping Negi. When Negi tried to perform a Pactio with her as 'Nagi', she already found out and changed Negi back into his original age. After knowing it was Akira and Yuuna's idea, she tells him that she wants to perform the Pactio with Negi as his true self, and not 'Nagi'.
- Yuna Akashi: The two seem to get along quite well due to them being natural born Mages. Like most of the girls, Yuna thinks Negi is very cute, but as time passes she begins to see him as her little brother and even Negi referred to her as a surrogate big sister. She often shows distress when she notices Negi getting hurt or into trouble and wants to assist him in some way. Negi acknowledges Yuna as a Mage and as a friend since he seems to have a great deal of trust in her. Yuna believes that it was fate that made them become partners as she stated her mother and Negi's father, Nagi, were acquiantances. Her relationship with Negi is very simiar to his relationship with Asuna.
- Makie Sasaki: Like Ayaka, she is also interested in Negi because she thinks he is cute. However, it all changed when she went to the Magical World. After Nagi's (which is Negi in disguise) identity is revealed to Ako, she then gets very confused and very worried. It gets even worse after her discussion with Akira, to the point where she should let Ako and Negi be together (although she is still not giving up on him). After Negi is in his Demon form, she did not hesitate to hold his hands and tries to ease his pain. She finally confessed to Negi before completing the Pactio with him, which makes her the second/third one of Negi's students to properly confess to him.
- Yue Ayase: Yue initially remained in the background at the start of the story. However, when Kazumi organizes a special game to kiss Negi, she decides to join Nodoka to help her win the game. However, when she was approached by one of the Negi clones attempting to kiss her, unexpected feelings begin to emerge, making her feel guilty in possibly cheating out Nodoka. Yue had a small crush on Negi in the beginning which later becomes love.
- Kaede Nagase: When Negi had fled into the woods during his conflict with Evangeline, Kaede found him while training, and helped cheer him up. She saw Negi flying off the next morning, but kept this a secret even from him until she helped Negi rescue Konoka at Kyoto where she fought and defeated Kotarou. After making a Pactio with Negi, she declares him as her new master while at the same time declaring herself as his servant, though she might have developed a small crush on Negi. Kaede acts as one of Negi's guardians as well as a surrogate mother figure towards him.
- Nagi Springfield: A powerful Magister Magi known as "The Thousand Master". He is Negi's father who was thought dead when Negi was born. Considered deceased by most, one night he mysteriously appeared before Negi to save him when his village was in danger, and gave him his staff. Negi believes his father is still alive, and follows every clue he finds about his whereabouts, determined to find him. One of Negi's reasons to work so hard is to become a master mage just like his father. Although several characters believe he is alive, no one knows where he is. In the end, Negi eventually finds and reunites with Nagi and introduces him to his students/comrades.
- Nekane Springfield: Negi's cousin (whom he calls older sister, since they grew up together). After his father disappeared, she and her parents took the orphaned Negi in. Her gentle personality is largely based on interpretations through disjointed flashbacks, so it is hard to identify precisely what she is like. What has been indicated however is that she took on more of a motherly role in his life, as at one time she even risked herself to protect him from harm. She is shown to be someone that Negi cares greatly for and respects a lot.
- Arika Anarchia Entheofushia: After the tournament in the magic world, it is revealed through an encounter with the Megalomesembrian Senator, that Arika (First mentioned during Rakan's movies of his adventures with Ala Rubra) is in fact, Negi's mother. Not much is known about her, other than she traveled with Nagi and Ala Rubra.
- Chao Lingshen: Assuming that what Chao Lingshen said about being a descendent of Negi Springfield is true, then it is certain that Negi has at least one child in the future and that one of his descendants gives birth to Chao Lingshen.
- Asuna Kagurazaka: She is somehow related to Arika, and is thus related to Negi. The full extent of this relationship is unknown.
- Touta Konoe: He is the genetic template grandson of Negi Springfield and is thus related to Negi. The full extent of this relationship is unknown.
- Albert Chamomile (Chamo): Negi's pet/familiar. A perverted, lingerie stealing, chain-smoking, talking ermine that Negi freed from a trap five years ago. Since then, Chamo has been fiercely loyal to Negi and admires him very much. He cares strongly for Negi and will fight to protect him, but he is not above using him to try to make a fast buck when possible.
- Kotarō Inugami: A wolf hanyō whose first encounter with Negi was as an enemy of his. Kotarō was one of the mercenaries hired to kidnap Konoka in Kyoto. After he was defeated by Negi and co., he was under the custody of the Kansai Magic Association, where his abilities to transform and summon wolf spirits were sealed. In order to challenge Negi for a rematch, Kotarō escaped and set for Mahora Academy. There he discovered a plan by Wilhelm and the Slime Sisters against Negi and lend him a hand to defeat them. For risking his life to protect Negi and his students, he was pardoned and decided to live in Mahora as an elementary school student. Since then Kotarō became Negi's rival, and one of his best friends.
- Anya Cocolova: Negi's childhood friend from his original hometown who also attended the magic academy that he graduated from. She too has a crush on Negi, despite her many claims to the contrary. Due to her lack of development, she feels threatened by girls with shapely bodies, declaring them to be her enemies.
- Fate Averruncus: The former member of Cosmo Enthelecheia and another one of Negi's rivals. He started developing an interest in Negi after the Kyoto arc. Before his last battle with Negi concludes, he said that he will let Negi to start his plan to save the Magical World and annouced that it is Negi's victory. Negi tried asking Fate to be his friend, to which Fate reject his offers (however, they get along well later). After school begins, he becomes the substitute teacher of Class 3-A. His current relationship with Negi makes Nodoka, Yue and Makie consider him as a somewhat love rival.