I'd suggest a "Car Talk" or "Ask This Old House" style call-in, submit-a-question format. Short, diverse segments that are listener guided (though sometimes the shows will have other prepped segments). These often border on the how-to side of things - but are deeply educational (and very successful) formats.
There are so many start up podcasts that focus on the origin of the founders/company and how awesome they are and they all blur into one. Rocketship, Tim Ferris etc. Please don't do a podcast like that.
You guys have the clout to do something a bit more special and unique than just cool interviews with successful founders. And you probably don't have time to do all of the narrative shaping that Gimlet and other media companies do to find all the "quirky" stories that fill time. That's why something based around office hours makes so much sense. Y Combinator's office hours on youtube are amazing. You've even expanded office hours to non YC companies because you see how valuable they are to the start up community. This is another way of realizing that value.
I listened to the podcast and they did often mention that they were broadcasting and gave a call in number, but I don't recall them ever taking a call. I'm not sure if no one ever called in or if they just never took a call?
