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?