Nerd Poker, a D&D actual play podcast that I've been really enjoying. Hosted by the comedian/actor/writer, Brian Posehn, we get to sit in on sessions of a 4E game he plays with fellow D&D folks. There is a real chemistry in the group with a fun banter of friends that is enjoyable to listen to. Getting to hear some laugh out loud comments and remarks from the crew is a bonus.
The setting is outlandish and definitely does not start with your typical, 'You all are sitting in a tavern...' One particular thing I love about the show is that the DM gleefully throws rules out the window and let's fun take over the wheel. It's refreshing to hear a group play D&D less focused on adhering to the rule book, and more about making fun (or at times agonizing) decisions on the fly.
So be sure to drop in and hear about the exploits of the goliath barbarian, Amarth Amon, and his companions. A fair warning the podcast encroaches on NSFW language at times. Give it a listen though. It's a hoot and an enjoyable departure from most typical D&D session podcasts.