There is no other person, be they human or hollow, who can bring out so many different feelings in Orihime, as the Cuatro Espada.
From being her jailor to becoming her companion in a world that was empty of companionship. The emerald eyed Espada had been with her for the whole time she had been Aizen's prisoner. Seeing him turn into ashes, unlocked the cache of feelings she had for him. Too late as she thought, but with the sudden appearance of Ulquiorra in the Living World, all bets are off again.
Roleplays

Relationship: Close friend
Ichigo is a close friend and classmate to Orihime. They've known each other for a very long time and have become a lot closer since they've fought together. For a long time she thought she had a crush on Ichigo but at a specific point in the last 2 years, she realized that this was just a smidgen of infatuation. Still, Orihime constantly worries for him and tries to help him in anyway she can.

Relationship: Close friend
Orihime admires the young Shinigami immensely. She likes to hang out with Rukia and talk about everything and the world.

Relationship: Acquaintance - likes her

Relationship: Friend - likes her

Relationship: It's complicated
Orihime has a very difficult hate/love relationship with the Ex-Captain of the Third. She had met him long after everybody already thought him dead. Orihime gave him his arm back, knowing fully well he could harm her at any time she still did it.

Relationship: Acquaintance - likes him