The present work was undertaken to examine and compare some biologically important properties of peroxo compounds of V(V) and W(VI) containing biogenic species as ancillary ligand. New anionic peroxovanadate(V) complex of the type Na[VO(O(2))(2)(triglycine)].3H(2)O (pV1) and a molecular peroxotungstate(VI) [WO(O(2))(2)(triglycine)].3H(2)O (pW1) were synthesized and characterized for the purpose and their stability in solution was ascertained. Studies on kinetics of inhibition of alkaline phosphatase activity by the newly synthesized compounds and series of dipeptide and amino acid containing peroxo complexes of vanadium and tungsten synthesized previously by us viz., Na[VO(O(2))(2)(gly-gly)(H(2)O)].H(2)O (gly-gly = glycyl-glycine), Na[VO(O(2))(2)(asn)].H(2)O (asn = asparagine), Na[VO(O(2))(2)(gln)].H(2)O (gln = glutamine), and [WO(O(2))(2)(gly-gly)(H(2)O)].3H(2)O, revealed that each of these species is a potent mixed-type inhibitor of the enzyme. Significant difference was noted between the peroxovanadium (pV) and peroxotungsten (pW) compounds in terms of their oxidant activity with reduced glutathione.