Peperomia is a species-rich genus, and one of its centers of richness and endemism is in the Atlantic Forest in Brazil. During field work in the Reserva Biológica de Duas Bocas, a protected area in Espírito Santo State in southeastern Brazil, a new species was discovered that is described here. Peperomia capixaba is a terrestrial herb with small, non-peltate leaves forming a rosette, each 5- (or obscurely 7) veined, with a concave lamina when living, having a cordate base and sinus overlapped by the lobes. This unique combination of features distinguishes it from the morphologically similar P. arifolia and related species. Peperomia capixaba is known only from the type locality, on the slopes of a mountainous region in Espírito Santo. Analyses of protologues and type images of related species resulted in novel taxonomic interpretations and nomenclatural changes in subgenus Multipalmata. Two new synonyms are proposed here: P. hydrocotyloides var. prolifera is synonymized with P. arifola, and P. rostulatiformis with P. clausenii.
