I highly recommend the podcast “Inside The Net” hosted by Leo Laporte and Amber MacArthur. They are featuring mostly technical topics concentrating on Web 2.0 and new trends and sites on the Web. They provide interviews with the people behind those sites and let you peek behind the scenes of the Startups running those sites.
The quality (both audio and content) is consistently high and I enjoy this podcast very much. It’s in my Top 5 list of favorite podcasts.