Oh, there are so many options! I'll just mention a few I've had success with in that tank size or smaller. Most Corydoras will breed happily in a tank that size. Same for probably just about any Pseudomugil species. I've bred P. furcatus, P. gertrudae, and P. luminatus. I've also bred the dwarf neon rainbow (Melanotaenia praecox) in that tank size. Ricefish haven't been mentioned yet. Just got a beautiful group of platinum Miyuki that are breeding in a 15 gallon. Of course, most "standard" livebearers (guppies, Endlers, platys, mollies).
A 20 long has such a great footprint, being long enough for fish to spread out and get away from each other when needed.