I'm going to say Ichigo+Rukia because of that first meet encounter they had. Ichigo depends on Rukia's wisdom and rukia always think she doesn't need inhigo to save her, but she really does. Orihime is more like a little sister to ichigo, but she doesn't see it like that. Deep down she loves him. If their was going to be a love scene or something at the end of the show most likely it would probably be Orihime because rukia is a Soul Reaper.