Usami looking at Misaki

Beware this part is based on the fact at how I perceive Usami’s thoughts in the manga, so it’s possible you won’t agree with me, but at least I try without having much information aside the manga and the anime, and I prefer the manga.
At the beginning what Usami feels towards the boy it’s definitely irritation, but he’ll help him just because Takahiro asked him to do so. But while the time goes on, he begins to support Misaki, and then he falls in love with him, after Misaki, knowing the love that Usami feels for his brother, gets angry with Takahiro for being so insensible and introducing his future wife to Akihiko saying:

You see I… wanted you to be the first one to meet her!
- Junjou Romantica, Volume 1, p. 36

And Misaki getting angry and then crying for him, makes him rethink everything and along that is his love interest, when he sees the reaction of the boy, who will become his new love interest, one he would not let go. I think one of my favorite parts where Usami explains exactly what he thinks about Misaki is when he is jealous, because of the senpai and tells Misaki:

You cried for my broken heart. I was sure I was hiding my trembling… but this kid I’d barley known for six months saw right through me. You wailed like a baby in front of me, even if we hardly knew each other. That’s when I realized… oh, he’s the one! So… when it comes to you, I can’t keep my composure. I won’t stand by… and let anyone take away the one I love again.
- Junjou Romantica, Volume 1, pp. 87-88



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Junjou Romantica: Usami and Misaki (c) Nakamura Shungiku