Ayato first meets Julis after attempting to return her handkerchief while she was changing clothes in her room. She challenges Ayato to a duel, and though it ended in a draw due to a surprise attack on her, she acknowledges his swordsmanship and talent. Despite her threats and cold attitude, she opens up to him and the two quickly become friends. The two of them decide to participate in the Phoenix tournament as partners.
Later in the series, Ayato is speaking everything that goes to him to her before to the other girls. It is hinted that Ayato's relationship with Julis is the strongest to the point that he takes countermeasures when he did something that will make her frown. Though he could be oblivious at times, he certainly can tell if Julis is mad at him. When Claudia asked Ayato in her room about him joining her team in the upcoming Gryps, Ayato's reply was "Sure, if Julis will join too." Though in their practice matches they may seem serious, Julis admits that she has no chance of winning if he is at his unshackled state. In episode 12, after Ayato and Julis win their match, Julis cares for him when he is in pain from his shackles. Ayato tells Julis he would always go through this pain to help her on her journey, and Julis says she will always help him to. The two almost kiss, but are interrupted by the rest of the girls.
Despite claiming to not care if Ayato was confessed to by other girls, she becomes agitated when other girls flirt with him, especially when she finds out about both Saya and Claudia's confessions, exhibiting a tsundere attitude.
Ayato's sister had a very good relationship with Ayato when they were younger. However, after going to attend Seidoukan Academy and after a mysterious occurrence in which she sealed away Ayato's powers, she has since then disappeared. Ayato goes to Seidoukan Academy in order to find her. Later in the series, Ayato found her in a coma state after his visit at Lieseltania thanks to him winning the Phoenix and wishing to find his sister.
Ayato grew up with her until she moved to Munich, Germany, due to her father's job. Saya is also willing to help Ayato when he is in need. Saya confesses to Ayato after considering Miluse's words, telling him that he could give her an answer on his own time as she simply wanted to express her feelings.
First having ran into her in the morning, Ayato quickly became friends with the small girl. Ayato admits that Kirin has the potential to be much stronger than him.
Later on, Kirin confesses to Ayato in the outdoor bath owned by the Toudou family.
Claudia, as Student Council President, gives Ayato much information, and can be very playful or serious with him. She later invites Ayato, Julis, Kirin and Saya to be part of her group for the upcoming Gryps Festa.
Claudia is shown to be in love with Ayato, her desire being to die while protecting him, later confessing to him in the hospital that she fell in love with him because of Pan-Dora. Despite confessing, she takes back her words soon after, telling him that she would confess properly sometime in the future.
Eishirou is one of Ayato's first friends and his roommate. Frequently selling information to Ayato for lunch and stuff, Eishirou is dependable and seemingly able to defend himself.
Ayato first meets Sylvia not knowing who she is, due to that fact that she is wearing a disguise. She lends him her help, as a powerful Strega, in locating Flora. They later went on a date on Volume 7 after Ayato accidentally agreed to her invitation during Volume 6. After being rescued by Ayato, she develops a crush on him. Her feelings become serious after Ayato pledges to help her solve her problem with Ursula Svento.