I feel Mario is better. I believe he has more combo potential, better fireballs, and seems a lot more sturdy.
I do not like Luigi's feel. I realize he's supposed to be a goofy character, but most of his moves have a gimmick, or are unreliable. For example, lets say you miss his forward-dash (not sure what I would classify this move as. It's the one where his arms flail and he tumbles forward)... you basically will set yourself up for a punish. Also, his side-special has a 1/10 chance of doing that "super" blast... I personally don't like characters who may rely on gimmicks (I'm looking at you, Game & Watch) to fight opponents or KO them. It just feels like I won by luck if I KO someone with Luigi's side-special. I also cannot think of too many Luigi combos. Mario can juggle opponents a lot with his u-air and follow up with an up-special or f-air... but I cannot say the same for Luigi.
Mario feels like a better character overall, due to my playstyle. I can never really get the hang of floaty characters.