High-performance liquid chromatography with diode array (LC-DAD) and electrospray ionization mass spectrometric detection (ESI-MS) was used to analyze phenolic compounds of two blackberry species (Rubus glaucus Benth. and Rubus adenotrichus Schlech.) growing in South America. UV-visible spectrophotometry was a valuable tool for identifying the class of phenolic compound, whereas MS and MSn fragmentation data were useful for their structural characterization. Ellagitannins were the major compounds, with sanguiin H-6 and lambertianin C being the predominant ones. The anthocyanin composition as well as the presence or absence of kaempferol glycosides can be used to distinguish the Rubus species studied. Flavonol hexoside-malonates were identified in both berries. Hydroxycinnamic acids were minor compounds and found as ferulic, caffeic, and p-coumaric acid esters. Similar contents were obtained by analysis of soluble ellagitannins and ellagic acid glycosides as ellagic acid equivalents and by analysis of ellagic acid equivalents released after acid hydrolysis