Great Chefs and Great Chefs of the World on Discovery. Awesome things were made on those shows.
Any/all of the classic Nicktoons, of course, along with Inspector Gadget, and other transplanted SMCs of the time that were moved to that channel; Classic Disney when they still aired the classic cartoons, and some of their adventure shows (Rescue Rangers and such). Hell, Loony Tunes and Tom and Jerry (though still airing on Cartoon Network again) were a sight for sore eyes. Freakazoid, Animaniacs. And what the hell, classic [adult swim] with Space Ghost: Coast to Coast and Cartoon Planet. And not to forget on Nick's part, some of the classic game shows and Space Cases as well as The Adventures of Pete & Pete.
Who's Line is it Anyway (all seasons) on ABC or Comedy Central (especially with the British episodes). Modern Masters on TLC (I think); some badass crafts made on that show. Dr. Katz, The Critic, Kids in the Hall, Classic SNL.
Hell, the days before having the ability to record live-TV, the internet and all it's media searching and such, hell, even a rather convenient guide on-command. I used to go by trial and error and time my schedules to watch shows I wanted to catch. And I didn't even have the convenience of knowing which episode would be on.
Ah, those were the days. Childhood was, so to put it, fun. It was a challenge to get what you want back then. Nowadays, it's just too damn easy. Not to sound like an old man, or anything.
Just have to emphasize the awesomeness of Pete & Pete with the first episode of epicness:
http://www.youtube.com/watch?v=LiFWyZjwykg