Just watched the AMA where @Leo was talking about an early Maxwell’s House episode where they discussed color theory. It doesn’t appear that these early episodes are accessible. The Twit.tv site only goes back to episode 55, and according to the wiki the episode he’s talking about is episode 4…
I had some fun looking through the Internet Archive, just out of curiosity, and I’m sure I’m not digging up anything people don’t already know. The good news is that a lot of snapshots of the twit.tv web site have been captured all the way from May 3, 2005, and they make fascinating reading.
What’s interesting is that the last snapshot taken in 2009 was on Nov 17, and there’s no sign of Maxwell’s House as a TWiT show on that date. The next snapshot is for Jan 5, 2010 (and the home page contains some interesting musings from Leo on the subject of funding the network). Maxwell’s House now appears in the list of shows, and the link goes to a twit.tv page archived on Dec 28, 2009 for MH 52, which shows MH episodes back to 50, exactly the same as the episodes held on the current site. That makes it look like the first 49 episodes of MH were not classed as a TWiT show, which is confirmed by the TWiT wiki which says that it became an official TWiT show in Dec 2009 http://wiki.twit.tv/wiki/Maxwell's_House .
There are show notes from ep1 onwards on the TWiT wiki, starting at http://wiki.twit.tv/wiki/Maxwell's_House_1
Each episode gives a location for a file page on odtv.me - this server seems to have disappeared but the pages have been archived by the Internet Archive, however the actual mp4 files were held on a server called kiwinerd.ca and the couple of files that I checked had not been archived by the Wayback machine.
My guess (based on history of other TWiT shows like TWiCH and TWiF) is that the show was streaming-only at first and didn’t transition to a podcast available for download until later. In the case of TWiF, some of those early streams were captured raw from ODTV and then made available for download, but there were no TWiT-edited podcast episodes.
That would be my guess for Maxwell’s House too. I can assure you that we don’t have any secret archive of early episodes hidden in the back of the server room…unfortunately.