1967-Spider-Man

The first animated Spider-Man series aired on ABC Saturday morning TV in 1967. Particularly remembered by many for it's funky 60's theme song and repeated use of stock footage, the series ran for 52 episodes and was endlessly rerun in the 70s on afternoon TV syndication.
It's popularity paved the way for several additional animated series, including one currently airing on Saturday mornings on the CW network.
There was a DVD set released in 2004 which is now incredibly expensive on the secondary market.