In Oblivion I joined the DB and found their quests to be among the most fun. And I feel that in Skyrim they will be even better. But I want to roleplay a character that isn't evil, more like chaotic and neutral with good tendencies. What could be a good motive for such a character to join the DB?
He could hold the belief that people the brotherhood are contracted to kill generally have it coming.
Alternatively, you could spin it as a "generally good" person being drawn into the webs of a dark cult. This adds a certain complexity to the morality game, since it assumes someone's morality isn't fixed, but constantly in flux.