Mine was winter soldier before he got buffed in 12.0. Used him quite a lot actually, helped me out in Act chapter 4 for my initial completion and he’s been at 4/55 for a long time. Still not duped though unfortunately.
My recollection is that my first 5* was Captain Marvel. At the time, I considered her not a bad pull. Poison immune and reasonably hard hitting. Also, I was happy to have any 5* champions.
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https://forums.playcontestofchampions.com/en/discussion/8754/ranking-up-5-champs#latest
My second was a Ms. Marvel (Kamala Khan).
On alternate account i got loki.
Star Lord on alt I think