Jason Calacanis has some real world empathy for entrepreneurs having been in the game since the web 1.0 era in NYC. His interviews and insights can be great, I often find myself reaching to write things down as I listen...
#2 This Week in Venture Capital
#3 Mixergy
All three are hit and miss. The best episodes of each are equally great because it's usually the interviewee that makes or breaks it.
Automate my Small Business - to hear interesting ways to put parts of your bis on auto pilot
Manager Tools - to learn how to manage the team you are building
NPR Planet Money - to know what is happening in the economy and how it might affect me and my bis
Note - most interviews are about an hour long so you'd have to listen to them over 2 commutes.
(they cover a much wider range than web tech though; some of their biotech and clean energy ones are particularly good)
I'm also a long time listener of This Week in Tech/Google with Leo Leporte. Buzz Out Loud and Today in Tech are also good daily tech headline podcasts.