Oxidative photocurrents measured upon irradiation by a 7-W visible light (wavelength 312-700 nm) demonstrated that the sulfo-polyoxometalate anion clusters [S2W18O62](4-) (18), [S2Mo18O62](4-) (1b), and [SMo12O40](2-) (2) may be activated photochemically to oxidize the organic substrates benzyl alcohol, ethanol, and (-)-menthol. In the case of catalytic photooxidation of benzyl alcohol to benzaldehyde in the presence of la, quantitative electrochemical methods have identified pathways for the oxidation of reduced forms of I generated during the catalysis. More generally, the oxidation pathways P(n+2)- + 2H(+) reversible arrow Pn- + H-2 and 2P((n+2)-) + O-2 + 4H(+) reversible arrow 2P(n-) + 2H(2)O have been evaluated by monitoring acidified acetonitrile solutions of the 2e(-)-reduced clusters by rotating disk electrode voltammetry under anaerobic and aerobic conditions, respectively. Neither of the reduced forms 1b(2e(-)) nor 2(2e-) reacted under these conditions. In contrast, 1 a(2e-) was oxidized via both pathways, consistent with its more negative redox potential, with the rate of oxidation by air-oxygen being significantly faster than that by H+. The present work demonstrated that the crucial step necessary to oxidize reduced catalyst in photocatalytic reactions involving the anions studied may be achieved or accelerated by application of an external potential more positive than the first redox potential of the polyoxometalate anion. Voltammetric analysis revealed that this in situ electrolytic regeneration of the reduced catalyst is an option that leads to a viable photoelectrocatalytic pathway, even when the H+ and O-2 pathways are not available.