A new photoelectrode system TiO2(ns)-VO2 for photoassisted electrolysis of water is described. The nanostructured TiO2 photoelectrode was prepared by the hydrolysis of titanium-tetraisopropoxide followed by deposition of thin film by spin coating. To prepare the TiO2(ns) VO2 photoelectrode, vanadium film was deposited on the TiO2(ns) film and subsequently oxidized in O-2 ambient. The TiO2(ns)-VO2 photoelectrode exhibited enhanced photovoltage and photocurrent of 680 mV and 11.0 mA cm(-2), respectively, whereas the TiO2(ns) presented 540 mV and 3.2 mA cm(-2) respectively. X-ray and S.E.M studies were carried out to monitor the surface and bulk characteristics of the TiO2(ns)VO2 photoelectrode. The rate of hydrogen production under photoelectrolysis was found to be 6 1 h(-1) m(-2) for the TiO2(ns) and similar to 13.01 h(-1) m(-2) for the TiO2(ns)-VO2 photoelectrode. The TiO2(ns) photoelectrode shows the improvement in the PEC characteristics due to higher quantum yield resulting from the structured nature of the material. The PEC improvement in the TiO2(ns)VO2 photoelectrode is due to the increase of range of absorption and the decrease of energy gap.