Mixergy, TWiT, This Week in Venture Capital, This Week in Startups, Sitepoint, Standford Entrepreneurship Videos (not sure if that is considered a podcast), Reporters' Roundtable
You?
It's obviously very far from startups, but I think every curious hacker would be interested and there is such a huge break between the episodes that it doesn't take too much time to follow it.
You can download the episodes here [http://www.dancarlin.com/disp.php?page=hharchive]. If you don't know where to start either try show 32 since it is a self contained episode or shows 27 through 30 if you have more time (and the stomach).
I especially like the schoolboy sniggering.
It's a networking podcast mainly focused on high end datacenter stuff, but also they have a wireless specific podcast periodically. If you're into hardware and systems engineering, it's quite interesting. They also get a lot of vendors on and really grill them.
Who Charted and Doug Loves Movies are pretty good 'brain off' entertainment as well. And I've listened to Planet Money and This American Life for years and years and years.
Dispatches: Former international correspondent Rick MacInnes-Rae talks to his international correspondent friends - http://www.cbc.ca/dispatches/
Ideas: One hour lectures and discussions with people who think deep thoughts about a wide variety of topics - http://www.cbc.ca/ideas/
I also regularly keep up with the Slate Political and Pop Culture "Gabfest" podcasts, although they can be a bit dry and elitist at times.
For pure entertainment, I like Marc Maron's WTF podcast, and The Moth is also great if you like shows like "This American Life" but can't always commit to a whole hour.
Also, I recommend Too Much Information (http://tmipodcast.com/) -- Interesting topics and wry humor, its a good listen.
http://techzinglive.com/ http://thechangelog.com/ http://5by5.tv/founderstalk
In Our Time, a BBC radio podcast focusing on history.
PBS Frontline (a tv show, not a podcast) streams all their shows online. Great for current events.
The Economist Audio Edition requires subscription to magazine, but if you want to catch up on the entire world in a couple of hours, this is the way to go.
"A weekly podcast tracing the history of the Roman Empire, beginning with Aeneas's arrival in Italy and ending (someday) with the exile of Romulus Augustulus, last Emperor of the Western Roman Empire."
The single funniest thing I've ever heard.
Also - Monocle Weekly - These are the guys that make Monocle magazine.