Even though I've never read an actual comic with that lineup (besides a flashback in Thunderbolts #9) there's an Avengers lineup I've always been intrigued by, the one called "Cap's Kooky Quartet".
It was Captain America, Hawkeye, Quicksilver, and the Scarlet Witch, the last three making their first appearances as part of the team. The first time I'd heard of them was Avengers #27 (the second volume, with Busiek/Perez), because it was a 100 Page Monster, with various old issues as extra material, and sense the actual story in that issue dealt with a new lineup, so did most of the reprints. One of the reprints actually went through the history of the Avengers lineups, as part of a news broadcast (being watched by Benjamin Grimm, no less). As an aside, I like that Avengers lineup changes are so publicly announced that the media reports on them.
During the news report, there was a mention of a time (Avengers #16, I think) when Thor went back to Asgard, and Giant Man, Wasp, and Iron Man all had personal business that meant they couldn't be Avengers. So Iron Man sponsors this hotshot sometime foe of his, and Pietro and Wanda just show up, asking for an opportunity to change their ways. Poor Cap is coming back from a mission with Rick Jones in some South American country dealing during all this, and gets back just in time to find out he has to lead a cast of rookies. Good luck, pal.
I think the thing that sold me on it was that as the newscaster mentioned this roster, they had a picture of that squad fighting Dr. Doom. I remember gawking at that, wondering how that team could beat a person of Doom's power (besides the obvious answer of "It's a Doombot"). I know the Scarlet Witch was set up where she could pretty much do whatever the plot requires, but it still seems like a woefully underpowered lineup for the Avengers (which makes me chuckle when I think how people said the same thing about the pre-Sentry New Avengers lineup). Which is part of the attraction, I think. As the Avengers, they face severe threats, and it's fun to see how teams overcome that with strategy, teamwork, luck, or whatever. It's part of what I've enjoyed about what I've read of Tony Bedard's work on Exiles, the team doesn't win through overwhelming power, but through some usually clever plan. It's that "gritty underdog" archetype so common to sports movies.