An inorganic-organic complex with a vanadium-substituted polyoxometalate 1, formulated as [Cu(phen)(2)](2)PVW11 O-40 was hydrothermally synthesized. Complex 1crystallizes in the monoclinic P2(1)/c space group with a = 25.9932(12) angstrom, b = 11.9889(6) angstrom, c = 23.2672(11) angstrom, beta = 113.6750(10)degrees, V = 6640.5(6) angstrom(3), R = 0.0312, and Z = 4. Complex 1 is constructed from a Keggin-type anion PVW11O404- coordinated to two [Cu(phen)(2)](2+) units. One [Cu(phen)(2)](2+) unit is coordinated to a terminal oxygen and the other [Cu(phen)(2)](2+) unit is coordinated to a bridging oxygen of the polyoxoanion. Redox activities for both the tungsten and vanadium centers have been observed using cyclic voltammetry performed on 1-bulk modified carbon paste electrode (CPE). It was found that 1 presents good electrocatalytic activities not only for the reduction of IO3-, NO2-, and H2O2 but also the oxidation of L-cysteine. Complex 1 also shows intense luminescent properties arising from ligand-to-copper charge transfer and oxygen-to-vanadium charge transfer at room temperature in the solid state. (c) 2008 Elsevier Ltd. All rights reserved.