#2 Lucha Bros

Lucha Bros are arguably the best tag team in the world today, and while seeing them in the main event of the first TV show makes sense, it's probably the most anti-climactic choice for All Elite Wrestling.
After All Out, the duo of Fenix and Pentagon have faced The Young Bucks three times in the first four shows for AEW, and doing it again would certainly be overkill, but you can't discount them as an option.
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We've not seen them interact with Chris Jericho during the run of AEW so far, so the story would have to be a good one to bring them together, but at this point, it's not likely to be these two.
However, given their star power and abilities, plus their chemistry with The Bucks, it's definitely possible, but right now, their future in AEW may be as singles stars, so we'll just have to see.