A tetranuclear cerium-containing polyoxometalate, TBA(6)-[{Ce(H2O)}(2){Ce(CH3CN)}(2)(mu(4)-O)(gamma-SiW10O36)(2)] (I, TBA: tetra-n-butylammonium), showed a unique intramolecular multiple electron transfer (Ce3+-to-POM(W6+)) on irradiation of visible light (lambda > 400 nm). This could induce hydrogen (H-2) evolution using alcohols as the electron donors, and a high turnover number (TON) of 1960 was achieved. Moreover, I could be reused without an appreciable loss in its catalytic performance.