Well i'm not sure what qualifies as "best" in this regard, considering one's feelings towards a couple is very subjective and what one finds attractive in a romance others find repulsive.
I'll just say that in DC, I like Lois and Clark. They just complement each other nicely and they support each other in the hardest times.
In Marvel...Ermm...The one couple where they haven't discussed, cheated, o beaten each other? Anyway I like Wolverine/Rogue, and yes, I know it's crack. Do tu think I care?