Ha...'niisan'. XD

Favorite big brother characters...I never thought of them before. :O

I can think of Ichigo from Bleach, he has two cute little sisters.

Does Neji count as a "big brother" for Hinata, all technicalities aside? >>;

Ace from One Piece, he and Luffy were really close.

Kaname from Vampire Knight. He loves Yuki...in more ways than one. xD;

Edward Elric, of course!

Sokka from Avatar.

...there are probably others, but this is a good list for now? XD;