Peperomia is one of the largest genera of basal angiosperms, with about 1,600 species, distributed pantropically. The Brazilian oceanic island of Trindade is located about 1,200km off the Brazilian coast; its maximum altitude is 620ma.s.l. and its area is 9.28km². Among the 113 species of vascular plants reported for Trindade Island there are two species of Peperomia: Peperomia beckeri, an endemic species known only from the type specimen; and Peperomia glabella.We re-evaluated specimens attributed to P. glabella from Trindade Island and compared them to specimens from the continent. The comparison included morphological analyses of the vegetative and reproductive organs, and a molecular phylogenetic study using the molecular markers trnK/matK and ITS. The trnK/matK marker showed significant differences between Peperomia from the mainland and Trindade. Together, these studies showed that the Peperomia occurring on Trindade is a species that differs both from those previously recorded on Trindade Island and from those on the continent, leading us to describe a new species. Peperomia segregata is endemic to Trindade, and would likely be considered critically endangered according to the IUCN criteria.