Five new species of Psilocybe from the Caribbean are described: P. caribaea, P. egonii, P. subpsilocybioides, P. zapotecoantillarum and P. zapotecocaribaea. All except P. zapotecocaribaea, which is known only from Martinique, are native to Puerto Rico. Psilocybe guilartensis, previously described from Puerto Rico, is the most commonly collected species of Psilocybe in Puerto Rico. New information on morphology is provided for P. guilartensis, and an emendation of the species circumscription is presented.