Seventeen herbal dietary supplements, marketed as natural substances for the enhancement of sexual function, were analyzed by diffusion ordered spectroscopy (DOSY) (1)H NMR. The method allowed a global analysis of the samples with detection of both active and inactive ingredients present in these complex matrixes. Eight formulations contained compounds related to the synthetic phosphodiesterase-5 inhibitors. Sildenafil, tadalafil, vardenafil, hydroxyhomosildenafil, thiosildenafil, and the newly identified adulterant thiomethisosildenafil were detected. Quantification of these active ingredients was carried out by HPLC or NMR. In addition to these actives, about 30 compounds or excipients were characterized. This study ended up with a three-dimensional DOSY-COSY (1)H NMR experiment on a herbal formulation which provided both virtual separation and structural information.