I'm in on this, if nothing else I'll provide color commentary and police the channel...though if we've got some folks in the Northeast forming a group, I'll show up.
If it's just me by my lonesome, I'd take it upon myself to clear classic as Sonic in Brawl (...maybe intense boss battles and tt's too? Perhaps I could get in contact with a pro Sonic for a few dittos or even a token Mario/Sonic standoff, I understand we want to keep Smash's bit short and sweet, but all the same I think it would be entertaining) since that's more of a diversion and doesn't necessitate the presence of a congregation, while at the same time not running into more complex things other players will be doing.
Anyways, this is meant as an exhibition, so we should consider the audience and more clearly define our goal. Right now, we're at an unhealthy middle of "flashy with skills but raw completion too". Seeing someone clear Sonic Advance 2 as Sonic in a flash is great fun, as is watching Sonic explore the subtler nuances of the game, but the hackneyed combination of "watch Sonic run as fast as he can on a rigidly described route and then excrutiatingly clear several special stages" isn't so hot. Pick a crowd, and stick with it.
On the note of games requiring multiple playthroughs as different characters to unlock the final bosses: why not have a few players synchronize their runs with game saves at different points upon which each character is unlocked? For example, in Advance 2 one player would run through Leaf Forest as Sonic from the beginning while another has a file with Leaf Forest Zone completed and simultaneously plays through the game, yet another playing with Tails loading from Ice Palace, etc. with a split feed broadcasting everything...for a really trippy effect, each run as a different character could begin exactly when the Sonic player 'unlocks' them by clearing the zone in which they appear. If nothing else, I think the idea of premade saves should be carried over for 'last' stories in the like, nothing's lost in transition just because one or two bits of grinding weren't done.
I'd say more, but I'm drained, and I hope it shows.