New peroxovanadate (pV) complexes anchored to soluble polymers of the type, Na-3[V2O2(O-2)(4)(carboxylate)]-PA [PA = poly(acrylate)] (PAV) and Na2[VO(O-2)(2)(carboxylate)]-PMA [PMA = Poly(methacrylate)] (PMAV) have been synthesized from the reaction of V2O5 with H2O2 and the sodium salts of the respective macromolecular ligands at pH ca. 6. The compounds were characterized by elemental analysis, SEM, EDX, TGA and spectral studies. In PMAV, the pV moieties are anchored in monomeric form to the polymer chain through unidentately co-ordinated O (carboxylate) atoms. Carboxylate groups of PA chain co-ordinate to V(V) centres, in a bridging bidentate fashion leading to the formation of dimeric pV structures in PAV. The PAY complex efficiently mediated bromination of organic substrates in aqueous-organic media at ambient temperature. Complex PMAV, was inactive in bromination under analogous conditions. The compounds are relatively resistant to degradation by the enzyme catalase compared to its natural substrate, H2O2. The polymeric complexes along with the free polymer and neat DPV were screened for their antibacterial activity against Staphylococcus aureus and Escherichia coli. (C) 2008 Elsevier Ltd. All rights reserved.