Caamembeca (Polygalaceae) is a genus of 13 species endemic to South America. The genus is morphologically distinctive, e.g. supported by the putative morphologic synapomorphy of paired glands in a stipular position and on the rachis. However, its monophyly has not been robustly tested as only four species have been included in previous phylogenetic analyses. We present a phylogenetic analysis of 11 species based on nrITS, matK, the trnL intron, and trnL-trnF intergenic spacer. Relationships among Caamembeca species are discussed, and three new combinations are made, Caamembeca amazonensis, Caamembeca autranii, and Caamembeca formosa, providing an improved understanding of the genus.