No, Sion doesn't love Itae she just thinks of him as a younger brother. A while before, her memories of her past life flashes back and so for a while she thought she liked Itae but that was just her past self's feelings for Itae's past self.
Ok sorry I got Yoon Kyeom and Sion mixed up- Yoon Kyeom thinks of Itae as a brother a has feelings for Islot. Sion doesn't like Itae though, she was in love with Itae's past self, who is basically a completely different person from Itae.
Haven't read everything, but I surmise, Sion loves Itae, and the vessel Yoon Kyeom loves daddeh Islot? Is that it??.