Tsuyuno and Aya are classmates. Tsuyuno first reaches out to Aya after realising that she has been contacted by the Mahou Shoujo Site and the two work together to find out the true meaning of the tempest. Over the course of their partnership, the two become very close "friends".
In Chapter 104 and Chapter 105, it turned out that Aya and Tsuyuno were twin sisters of a day different. The real mother died soon after he was born, his real father was unknown, his relatives refused to underwrite and he was taken down as a adopted child in a separate family, and was brought up.
Aya was informed of the fact that Tsuyuno was his twin sister from Juuni, I think that I will be shocked by having lost my sister as my best friend, she is delighted that she was connected to Tsuyuno by fate, from the bottom of my heart He smiled.
He is Tsuyuno's classmate. Although he is not as close with Tsuyuno as he is with Aya, he despised and dislikes Sarina Shizukume and her friends who bullies Aya.
Tsuyuno is secretly seeing that he is in love with Aya.
Soji Odano is the criminal that murdered Tsuyuno's family. Before becoming a Mahou Shoujo, Tsuyuno lived in fear of Odano, however after becoming a Mahou Shoujo she took matters into her own hands to prevent him from hurting her and to get her revenge. She keeps him in her apartment to torture him, but Sarina killed him which made Tsuyuno upset.
Rina and Tsuyuno met online. They decided to team up together and nicknamed a murderer who was killing Magical Girls to steal their sticks the "Magical Hunter". Then for unknown reasons, they lost touch. Tsuyuno thought that Rina was killed by the "Magical Hunter".
Then after Tsuyuno teamed up with Aya, Aya got confronted by Rina who was in disguise and trapped Aya in a box to kill her and steal her stick, Tsuyuno stopped time but was shocked when she saw that the 2 inside the box were not affected and she encouraged Aya to use her stick on Rina. Aya, who was hesitant to use her stick said that she might kill Rina but Tsuyuno assured her that she won't die since she stopped time, Aya then shoots Rina and got teleported to the place where Aya found the cat she cared for.
Tsuyuno and Aya began to question Rina, which Rina didn't answer at first before getting threatened by Tsuyuno and finally answered and Rina collapsed because of overuse of the sticks' powers. After she recovered thanks to Kosame Amagai, the four decided to team up with the other Magical Girls which Rina joked to the two that she didn't kill them in their sleep for that reason. After they teamed up Rina and Tsuyuno became close friends. Rina also showed her appreciation to Tsuyuno as shown in Chapter 55.
Sarina Shizukume and her group of friends, Erika Kaijima, and Ai Kawano are disliked by Tsuyuno. Tsuyuno dislikes Sarina and her friends, despised as "human garbage" "bitch", but after Sarina had reformed to a certain extent, she began to change her mind.
Mr. Yatsumura was the father of Tsuyuno. As a child, she loved him dearly, but when he as well as Mrs. Yatsumura got killed, she fell into despair. She became a magical girl because of her parent's deaths effecting her life. She promised herself that she would torture the person who killed her parents. Before she could kill him, Sarina Shizukume killed him on accident with her stick.
Mrs. Yatsumura was the pregnant mother of Tsuyuno. She shared the same fate as her husband and was killed by Soji Odano. Her fetus was also killed as well. We might be able to tell that they had a good relationship because Tsuyuno lived all her life just for avenging them.