Three c-glutamyl dipeptides have been isolated from Petiveria alliacea L. roots. These dipeptides include (SC2RC7)-c-glutamyl-Sbenzylcysteine together with two diastereomeric sulfoxides, namely (SC2RC7RS)- and (SC2RC7RS)-c-glutamyl-S-benzylcysteine S-oxides (c-glutamyl-petiveriins A and B, respectively). Their structures and absolute configurations have been determined by NMR, MALDI-HRMS, IR and CD spectroscopy, and confirmed by comparison with authentic compounds obtained by synthesis.