Well, it had a lot of decent PC ports because the Amiga was still modern when it came out. So there was a good version of Pirates, Frontier, Civilization, Alien Breed 3D, Roller Coaster Tycoon, and a host of stuff from Psygnosis and the Bitmap Brothers to name just a few. Actually Psygnosis was bought by Sony as a PlayStation developer because of their work on the Amiga line of computers including the CD32. Their last independent work was done for this console.
The best game is a pretty large RPG called Liberation. (Captive II) It took place in the future and involved some decent 3D for the time. This was back in the day when the European developers made RPG titles. For the most part they don't do that anymore. They had really interesting story arcs. It costs too much for a developer in, say, Hungary to develop a game today. But back in the day it was cheap to produce titles for a console like this.
A lot of the stuff that was released on the Atari Jaguar were originally CD32 titles. Zool, Soccer Kid, Pinball Fantasy, etc. It was a major game system in the UK and at the time the UK had a lot of development companies. Most games were designed for the Amiga, so they worked with a mouse or combination keyboard and 1 button Atari style joystick. The gamepad had limited support. It worked fine, but it was cheap and crappy. I've used much worse though.
The CD32 was Commodore's second CD system. They released the first, which was the CDTV. I have one of those as well. It will show up here eventually. It's a larger system, so it's in a different storage area.