Yes, definitely! I had a couple of these (City/Balance of Terror and Tribbles/Last Battlefield) and also bought that Gateway release of Space Seed. I couldn't afford to buy all five. Trek hadn't been on for several years in my location, so those were my only "fix," apart from one episode I had audiotaped when I was 8 and the various tie-in products.
I remember that Vol. 1 was The Menagerie and Vol. 2 was Amok Time/Journey to Babel, but I can't quite remember what Vol. 3 was. Was it The Enterprise Incident/The Immunity Syndrome?
Actually, Volume 3 was my favorite! It was "Mirror, Mirror" and "The Tholian Web".
The other thing that always stuck with me is that they cut the pre-credits opening and the opening credits from the second part of "The Menagerie", opening with the Enterprise shot and Kirk's log entry. Plus, the sound quality on that was really muted!