David Heinemeier Hansson Flosses Weekly
There's a great interview with David Heinemeier Hansson @DHH, one of the founders of http://www.37signals.com and the guy behind http://www.rubyonrails.org, on FLOSS Weekly 79: http://twit.tv/floss79. He talks a lot about developing and releasing the rails open source initiative into the world and does a bit of rails evangelizing (deserved), reminiscing about 37signals and talk about his dev environment. Good stuff.
BostonPHP Podcast discusses JQuery, barackobama.com, High Traffic of Facebook, et al
BostonPHP has some great podcasts in their archives. Among the notable are two covering JQuery, a conversation with one of the folks behind barackobama.com and a talk by a guy from Facebook covering strategies for 'high traffic' php sites (including how they deliver billions of images per day, obscene stuff.) Listening to people talk through code doesn't exactly lead you to mastery, but it does lay some broad conceptual strokes and ranks among the highest forms of nerdy enjoyment.