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I highly recommend Radiolab (http://www.radiolab.org/), it's one of the most respected podcasts out there. It's changed the way I see the world.

The BBC's "In Our Time" [1], a weekly discussion of history, science, literature, culture -- brilliantly moderated by Sir Melvyn Bragg. Effortlessly intelligent and always entertaining.

[1] http://www.bbc.co.uk/programmes/b006qykl

I have a show called Product People: great products and the people who build them (software, apps, ebooks). http://productpeople.tv

Also highly recommend: Startups for the Rest of Us.

KEXP has some nice music podcasts