Skeptic's Guide to the Universe -- This one is about skepticism, critical thinking, and science. Lead by a neurologist at Yale.
Radical Personal Finance -- Lots of variety in topics (personal finance, entrepreneurship, sustainability). Very long. There are a lot of things I like, but I also prefer when he stays away from politics and gender issues. I skip the parts where it gets very libertarian or goes on about marriage/Christianity/why his wife stays at home with the kids.
Tropical MBA -- Two location independent entrepreneurs. Great if you're interested in entrepreneurship.
The Voluntary Life - Short, but I still like it. Focuses on personal freedom.
Stuff from NPR.
I wish had some entertaining, female focused, non biz/finance podcasts I liked.