Vitamin, the producers of the Web2.0 podcast have an excellent how-to on using Skype in a podcast.

So you want to be a podcast superstar? Well, while this article might not make you a superstar, the aim is to help you record quality audio using Skype. Skype recording can be a tricky, but the benefits far outweigh the time investment it takes to learn. We use it on the Web 2.0 Show podcast to capture our interview audio and it has allowed us to interview some very big names without being in our interviewee’s location. Or running up large phone bills. This article will cover both Mac and Windows based recording techniques, and we will post follow-up articles covering post-production of the audio and how to upload and track your podcast.

Interestingly, on Windows they use HotRecorder instead of the more commonly used Skylook.