The BBC put metadata for all the Peel Sessions online a while ago, which I'd forgotten about until Erin Staniland and Kelvin Luck made an interface to the data for Hack Day London 2007. The whole database is available under a CC licence - I found that after I'd already scraped all the pages, of course.
Here's my attempt at a different representation. At the moment it combines information from the BBC and last.fm, and exports XSPF playlists of each session.