The photoresponse of bare TiO2 and TiO2/WO3 hybrid electrodes was studied in a photoelectrochemical cell with VO2+ in 3 M sulfuric acid as the electrolyte. Linear sweep voltammetry study on both electrodes under AM1.5 illumination revealed a significant photoresponse enhancement compared to photolysis of water. This is attributed to the hole scavenging process initiated by quick redox reaction and depressed charge recombination at semiconductor/liquid interface. The photocurrent was boosted remarkably by factors of 57 and 78 on the bare TiO2 and TiO2/WO3 hybrid electrode, respectively, when the VO2+ concentration increases from 0 to 1 M. This finding might render this approach a very promising way of solar energy conversion and storage. Photocharge/discharge process was also discovered on the WO3 surface under different energy level of irradiation, leading to a deteriorated photocurrent. Published by Elsevier B.V.