TechZing is one of my favorites. It's semi-educational though retains an informal, discussion format in the main (that is, it's not just lectures): http://techzinglive.com/
I am really loving TechZing so far. I have been trying to work through the backlog after I found it a few weeks ago.
It's not always about startups and entrepreneurship, but I like it a lot more than other podcasts that are constantly rehashing the same "top N ways to do X with your startup" content. I would say its more about bootstrapping, which is more interesting to me anyways.