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Spoiler: Suho fell for the FL EXTREMELY early on (since she recommended a comic book to him, which was in one of the first chapters), which he tells her in chapter 59 when he confesses his feelings for her before moving to Japan. The other semi-ML also falls for the FL before she gets any romantic feelings for him.
I think Ahin fell in love with Vivi significantly earlier.
Chapter 167: They finally told each other that they love each other (they have for a while, but they never worded it properly; they had only told each other that they like the other person).
Chapter 169: We find out that they met once when they were around 5 years old, and it appears that Ahin fell in love then already. He even got the feeling that he would and wanted to marry a wererabbit (he found out that Vivi is one)
He fell in love with her at first sight when they first met when he was a kid
Carlisle falls for Elena the first time they meet at 10 and never stops loving her (his love for her is what gets him through the war)
Kago fell in love at first sight with Eileen when he was 11 years old
Kiyu fell for Lily in chapter 14 when Lily saved him in class, whereas Lily fell for Kiyu in chapter 52 when she finally managed to get a proper look at his face, and he was looking right at her, smiling affectionately.
He fell in love at first sight with her
Father, I don't Want this Marriage