Psychotria subg. Heteropsychotria Steyerm. has been shown by morphological and molecular analyses to be polyphyletic. Most of its species, including its type, belong to Palicourea Aubl. (“Pal.”). Thirty-two species of this group are reviewed here, and 17 species in Psychotria L. are transferred to Palicourea and one to Rudgea Salisb. Two replacement names, Pal. agudeloana C. M. Taylor and Pal. tabayensis C. M. Taylor, are published. Taxonomic studies here clarify circumscriptions of similar, often-confused species for several distinctive species groups found variously in Mesoamerica and the Andes: the Palicourea aschersonianoides group, the Palicourea galeottiana group, the Palicourea sulphurea group, and the Palicourea tristis group. Three new species of Palicourea are described: Pal. aschersonianula C. M. Taylor, Pal. gonzaleziana C. M. Taylor, and Pal. wachterae C. M. Taylor. Nineteen names are newly typified, and infrageneric classifications are noted for the species of Palicourea studied.