Mormyridae, a species‐rich family endemic to Africa, remains taxonomically understudied. This has been the case for the genus Pollimyrus Taverne, 1971, which hinders further understanding of the distribution, ecology, and conservation of its species. Therefore, an in‐depth morphometric comparison of all currently valid species is carried out using most of the available type specimens. Species delineations were re‐evaluated, and four species new to science described: Pollimyrus ibalazambai sp. nov. (the Luki River, the Democratic Republic of the Congo), Pollimyrus krameri sp. nov. (the Lugenda River, Mozambique), Pollimyrus vanneeri sp. nov. (the Kouilou‐Niari River, the Republic of the Congo), and Pollimyrus weyli sp. nov. (the Buzi River, Mozambique). In this study, Pollimyrus guttatus is confirmed to belong to Pollimyrus, whereas Pollimyrus eburneensis and Cyphomyrus plagiostoma seem more similar to species allocated to other genera. No or only little morphological differences were found between the type series of several species, which could indicate the need for synonymization of these species (Pollimyrus cuandoensis with Pollimyrus marianne and Pollimyrus nigripinnis with Pollimyrus pulverulentus). As such 20 species are currently morphologically identifiable in the genus Pollimyrus. The present study highlights the critical need for further synthetic efforts and new collecting efforts across Africa for this and other Mormyridae genera.