No, he certainly wasn’t in love with him from the very beginning. He was definitely interested in him and had been somewhat captivated by him since Pilsang first caught his attention. However, I believe that the moment he first mentions finding Pilsang cute marks the point where his feelings begin to evolve into genuine love.
He was also clearly surprised by the fact that he found Pilsang cute, but he just shook it off. And that's because in Korean culture, they say that when you start to see someone as cute, it’s a sign that you’re beginning to fall in love with them ~
So he kinda was in denial and chose to believe he only found Pilsang cute cause he reminds him of a pet...lol
It wasn’t so much jealousy as it was possessiveness. Pilsang had become "his" toy, in a sense, someone he and only he could play with and no one else, Jooeon acting just like a spoiled child unwilling to share his possessions.
At the same time, he genuinely didn’t want Pilsang to have sex with randoms, especially since he was also involved with him and didn’t want to risk catching an illness.
So in conclusion, Jooeon was definitely captivated by Pilsang from the moment he saw him sacrifice himself for Hajoon. However, i wouldn't say it was love at first sight, cause it clearly wasn't, instead, he gradually came to appreciate him and fell in love with him over time !

I feel like Shin Jooen's been in love with Yoo Pilsang from the beginning but just doesnt realise it's love because he's never really experienced it. He can make people fall in love with him but he's never felt it himself. Idk, I feel like that 'absurd lust' he felt in the beginning was a sign. And what he thinks of Yoo Pilsang too, a man who managed to stay kind despite his upbringing and environment. You wouldn't think so highly of someone you're just messing around with.