I'm actually reading it right now and it's kinda neat reading the ca. 2006 viewpoints of serial entrepreneurs who have been hugely successful (again) since these interviews were recorded.
Imagine what Evan Williams (Blogger/Twitter) and Paul Buchheit (GMail/Friendfeed) would have wanted to talk about three or four years ago. You can see the seeds of their soon to be successful new businesses in every line of these two interviews. Really a great bit of history.
EDIT: 21 minutes in the topic shifts to "What can big companies learn from startups?"
It's the best book a young entrepreneur can read ... there's isn't a universal recipe for success (it's actually funny that in Founders@Work the interviewees often have contradictory view-points), but you can learn a lot from it.
Really looking forward to reading it now.