Here is an archive of all the past top five lists I've one over the years.
Marvel just released an upcoming cover of All-New, All-Different Avengers showing Captain America and Thor kissing. That made me think about all of the Avenger teammates over the years who have been couples, so I figured I'd rank them. I'm only counting the "main" Avengers title, not Avengers Academy or Young Avengers (Wiccan/Hulking would be high on the list if I were).
Here's the thing. Avengers couplings tend to end badly, or begin badly or are just bad ideas all the way through. So this is actually a surprisingly difficult list to put together. Here, then, are the couples that did not make the list that are worth mentioning, at least:
Hercules/She-Hulk (not much there)Starfox/She-Hulk (also not much there, and also has the side problem of possibly being creepy with regards to Starfox's powers)Iron Man/Wasp (they dated for one issue)Spider-Woman/Hawkeye (this could have been something, but his solo series launched at around the same time and it never really worked out, since he was pretty clearly single in his own title)Captain Marvel/War Machine (not really an Avengers couple, but close. If their relationship was in an Avengers title, I might consider them)Swordsman/Mantis (this was just a weird relationship)Justice/Firestar (I don't really consider it an "Avengers" relationship when they had been together for, like, seven years by the time that they joined the Avengers together)Sersi/Black Knight (she practically blackmailed him into the relationship - not a good relationship)D-Man/Wasp (a relationship so torrid that I just made it up)Black Widow/Hawkeye (talk about a dysfunctional relationship - she uses him for villainy and then when she comes around to being a hero, she pretty much leaves him right away!)Hercules/Deathcry (she was basically a teenager, so it was a weird relationship)Wasp/Hawkeye (never made much sense)Scarlet Witch/Wonder Man ("I won't let you save your husband's soul, but now we're free to date!" "Okay!" How did his rather messed up plan WORK? Who the hell thinks that his behavior should have been REWARDED?)Tigra/Avengers West Coast (all of them were brief flings)Crystal/Quicksilver (I know they were briefly Avengers together, but it was reeeeally brief. I don't think of them really as an Avengers couple. And even if I did, they were not a good couple)Black Panther/Storm (similarly, they were barely together in the Avengers as a couple)Crystal/Black Knight (this is how messed up Avengers relationships are - she was married and he was in a sort of psychic relationship with another woman and this was still one of the most functional Avengers relationships)Havok/Wasp (probably the closest to the top five)
Smasher, the first Earthborn member of the Imperial Guard and Cannonball were a cute couple during Jonathan Hickman's Avengers run, but in Avengers World, they were given room to be even more adorable, like this issue, Avengers World #17, by Frank Barbiere and Marco Checchetto...
It's almost as if they have a nice, normal functional relationship. Are they sure that they're Avengers?
This is a tough one to omit from the top three, as I do like them as a couple, but as far as Avengers couplings go, they only lasted for, what, four years? Then they briefly got together, then she was dead for a dozen years.
Plus, I'm sorry, I just can't get behind a coupling where the guy finds out that his wife was raped and that she then let her rapist die and reacts THIS way (from West Coast Avengers #35 by Steve Englehart, Al Milgrom and Mike Machlan)...
"Yes, I believe the ghost of your rapist over you! This is something that I am saying for some reason! I am so mad at you!"
3. Hank Pym/Wasp
It is a tough call between this pairing and Hawkeye/Mockingbird. They both ended in divorce, but Hank actually struck Jan before they broke up. However, it is not like Hawkeye and Mockingbird split amicably either. Meanwhile, this relationship did last a pretty long time. They were a couple for years before they actually got married in Avengers #60, which, true to form for an Avengers relationship, was based around Hank Pym having a nervous breakdown and developing a split personality and Janet Van Dyne deciding, "Hey, now's a good time to lock this down!"
Yes, Cap, that's the ONLY way to find out. No other way but to become a member of the wedding (man, can you imagine how much Cap must cry at weddings?).
Wasp and Hank had a rough relationship, especially due to his mental health problems. Here, in Avengers #161 (by Jim Shooter, George Perez and Pablo Marcos), we see how bad it was getting...
(I don't know if Wasp was interpreting her therapist's advice correctly with her new costume)
Despite all of this, they manage to stay friendly after their divorce and have gotten back together a number of times. I think their longevity pushes them ahead of Hawkeye/Mockingbird (who have also gotten back together a couple of times themselves).
Go to the next page for the top two!