An overview of structurally characterized α-hydroxycarboxylatodioxo- and α-hydroxycarboxylatooxoperoxovanadates(V) is presented and the geometric parameters of the V 2 O 2 bridging core are discussed. The first case of a stereospecific formation of oxoperoxovanadates(V) is reported: The crystal structures of the isomeric compounds (NBu 4 ) 2 [V 2 O 2 (O 2 ) 2 (l-lact) 2 ].2H 2 O and (NBu 4 ) 2 [V 2 O 2 (O 2 ) 2 (d-lact)(l-lact)].2H 2 O (lact=C 3 H 4 O 3 2 - , the anion of the lactic acid) differ mainly in the arrangement of the V 2 O 2 core and in mutual orientation of the V O bonds. The complexes with achiral ligands adopt the same structural type as the complexes formed from a racemic mixture of a chiral ligand, while the structure obtained using an enantiopure l,l-hydroxycarboxylate is different.