Visible light driven water reduction is successfully achieved over the novel hetero-system NiO/ZnO. The capacitance measurement (C(-2)-V) of NiO exhibits a positive slope, characteristic of n type conductivity, from which a flat band potential of -0.80 V(SCE) and a density of 1.41 x 10(18) cm(-3) are obtained. The correlation of the energy levels indicates that the photo electrons react with adsorbed H(2)O molecules via ZnO interfacial mechanism. Two NiO compositions (4% and 10%) onto ZnO support are prepared by the impregnation technique. The electrons generated upon visible light in the conduction band of NiO, anchored uniformly on ZnO, diffuse to the interface for achieving the water reduction. NiO is photoelectrochemically stable by hole consumption reactions involving S(2)O(3)(2-) as sacrificial agent. The best performance is obtained in basic media on NiO (4%) with an evolution rate of 435 mu mol h(-1) (mg catalyst)(-1) and a quantum efficiency of 0.3%. The hetero-system has the thermodynamically force to drive the uphill reaction (S(2)O(3)(2-) + H(2)O + 2OH(-) -> 2SO(3)(2-) + 2H(2), Delta G(f)degrees; = 101.04 kJ mo1(-1)). (C) 2011 Elsevier Ltd. All rights reserved.