"Catuaba" is a popular herbal medicine from Brazil, and Erythroxylum vacciniifolium is a Brazilian endemic plant referred to as "catuaba". A sample of "catuaba" assigned the name Erythroxylum vacciniifolium from Paraíba was investigated in the ongoing search for new bioactive compounds from higher plants. To evaluate its activities and because of the chemotaxonomic importance of tropane alkaloids, a phytochemical investigation of the alkaloid extract of the bark of E. vacciniifolium was undertaken. Eight new tropane alkaloids (1-8) were isolated from the bark, and their structures were determined by high-resolution mass spectrometry and multidimensional NMR spectroscopy. This paper reports the isolation, identification, and structure elucidation of these eight new tropane alkaloid aromatic esters (1-8).