Orihime states very clearly in the chapter/episode "Goodbye Halcyon Days" that she is in love with Ichigo, when addressing his sleeping form:
"I wanted to be a teacher! And an Astronaut! And open a bakery! I wanted to go to the donut shop and ask for everything! And go to Baskin Robins and ask for every flavor! If I only had five lives, then I could live in five different towns doing five different things and stuff myself with five different foods...and fall in love with the same person five times over."