Kiyome entered Kouh Academy the same time as Rias, they appear to be on friendly terms despite her somewhat fear of Devils. At times Rias come to her for assistance about her knowledge over supernatural creatures as part of her Devil school requirements or if Koneko were to be unwell. They also appear to have a somewhat rivalry, such as when she ask to have Issei for a day on the condition if she wins their tennis match.
Kiyome came to Issei for assistance in breaking off her arrange marriage her father set for her by pretending to be her boyfriend, which he agrees to. As she watches him struggling to go through each challenge against her father for her sake and won, Kiyome begins fall in love with him, however she holds back her feelings after realizing how he feels towards Rias.
While Kiyome cares for her father and vice versa, she disliked how strict he was enforcing her to go through a marriage meeting despite her disagreement, Kiyome would go as far as to trick him into getting out of the engagement, such as pretending to already having a boyfriend.