Despite the cultural and economic importance of fisheries to communities in the region, the Mfimi is one of the least well-documented river systems in the central Congo basin. Here we present a preliminary listing of species collected during two surveys sampling 35 sites along the main channel, in major tributaries, and in some marginal habitats. A total of 2195 specimens representing 141 species were collected and archived at the American Museum of Natural History, New York, and in the teaching collections of the University of Kinshasa. Five species are considered as potentially new to science, and range extensions of numerous species into the Mfimi are recorded. Based on the data presented we conclude that the fish communities in the Mfimi share affinities with those of the Cuvette Centrale to the north, rather than the Kasai basin with which the river is currently connected via an inflow at the Kwa-Kasai junction.