Hercules and Hebe?
Apparently they've been together since Zeus married them upon Herc's apostesy. They've never officially split-up, they've just been separated.
Herc, it's widely known of course, has spent most of their marriage philandering (that's a fancy way of saying cheating on his wife). Herc's behavior is obviously less than ideal for a hero, but during the "Assault on New Olympus story-arc he and Hebe seemingly reconciled so we'll see if that is even remembered let alone used in Herc's future story-lines.
Personally, I like the idea of Herc pairing with many of Marvel's super-heroines (and some villainesses, too). Though this flys in the face of the heroic ideal, it fits well with Herc's rakish charm and flawed persona.
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