Early in my career, I was a regular listener to three tech podcasts: Java Posse, StackOverflow podcast, and Software Engineering Radio. All three were valuable to my career in different ways, but EconTalk has most affected the way I think.
For those who aren't familiar, the host of EconTalk is a professor of economics, so many of his conversations revolve around the world of economics, but since economics touches a lot of things, he ends up talking to a diverse group of people. He is very good at admitting his own bias on the one hand, and then argue against it on the other hand.
Also, I found History of Rome valuable - it's an interesting story, but it also helps cure the chronological snobbery of assuming that our times are vastly different from others.