I've been listening to podcasts for a while and I want you to listen to them too. Here's a list of my favorites.
Favorite episode: Brick Building Full of Lies
Again, I'm a huge Merlin Mann fan, so it's hard to not recommend this one as well. He and John Roderick just want to help you. Why won't you let them help you?
Favorite episode: Everybody Knew What Mr. Finnell Did
Deranged millionaire John Hodgman renders judgement on any dispute set before him. He's a genius of wit and I can't recommend this one enough.
Favorite episode: Out of REC-order
This is the canonical Great Podcast That Some Might Not Understand. Basically, it's absurd, well-edited humor. And it comes in at the middle. So, buckle up.
Favorite episode: Razzledazzle
This one isn't quite for everyone. It helps if you're already a fan of the Yogscast guys. Simon and Lewis are such a terrific duo and it's quite entertaining to just listen to them discuss anything. Also, don't miss Simon's voices. They're solid gold. It updates sporadically, so don't expect weekly episodes.
Favorite episode: Dungeons & Dragons Part I (sorry, no permalink)