Leaves of 15 Brazilian species of Psychotria, three of Rudgea and Palicourea rigida, were analyzed for their alkaloid and iridoid content. Alkaloids were found in three of Rudgea and 14 species of Psychotria, and iridoids were found in Psychotria leiocarpa, which produces asperuloside and de-acetyl-asperuloside. Palicourea rigida yielded no alkaloids but loganin was isolated. The results illustrate the significance of the alkaloids in the chemotaxonomy of some taxa of Psychotriaea. The phytochemical data indicate that the American species of Psychotria with Palicourea could be joined to form the genus Heteropsychotria.