In Feb 2006, Shout! Factory Studios released package of 4 DVD, named The Best of Electric Company, featuring best shows (not spidey-specific ) from 1971-1977. (EAN: 0826663512199 ).
In March 2006 they released another DVD named The Best of the Best of Electric Company (EAN: 0826663100662).
We're not exactly sure which Spidey episodes are on the show, but we'll see if we can get a hold of a set and keep fans informed.
(Info thanks to Scai)