He doesn't even think of her doing as something villainous, even from when they're a child he always looked up to her. He regards her as strong, chivalrous, and will do anything to fullfil their duty as nobles. For him she always do things that he wanted to do but didn't dare to, she's the perfect being he wished to be that it severely affected his confidence thinking he's a completely inferior being compared to his sister. It's to the point of obsession thinking that she will always do correct things and will never do any mistake, if her sister told her to die he will kill himself on the spot.
So the answer to that point is no, he never aware that she's trying to act "villainous" because from his viewpoint what she does is "chivalrous".