I've just been listening to a podcast of This American Life and I was wondering what the song was from the end of episode 218: "Act V" (at 56:11 of the 58:33-length podcast; originally aired on 9 August 2002; recently aired on 1 July 2011).
I searched around on the TAL website, but couldn't find a track listing. Then I remembered I could use Shazam on my iPad. Turns out it's "Desperado" by The Langley Schools Music Project on their album "Innocence & Despair".
Skip to 56:59 to hear the song in context.
Listen to the song on Grooveshark.