Oh my friend, it is ON! Of course since live albums tend to be kinda like "greatest hits albums" I don't own a whole lot, but I'll make due.
Stop Making Sense is at the top of my list, until proven otherwise. Its more then an album and video, its a total life experience. You've got the vastly superior version of Psycho Killer, there is the vast array of venerable side musicians, and above everything you've got the BIG SUIT!
My two runners up are:
10,000 Maniacs -- Unplugged
Nirvana -- Unplugged
Yes, both of these albums come from the Unplugged phenomenon that was sweeping across the country in the earlyl 90s. Yet these two bands embraced the gimmick and ran with it creating an aural experience that took the bands to the next level. I think the biggest reason I enjoy these albums so much is that both albums were put out after the band broke up/Natalie Merchant left. Both groups played with an intensity and emotion that seems to say "this is one of our last outputs as a cohesive unit and we're gonna take it to another level."
Alright, lets see your cards folks!
~~Willis, strives to own a Big Suit someday