This paper deals with the current transport mechanism of solid state photoelectrochemical cells of ITO/TiO2/PVC-LiClO4/graphite as well as the physical properties of a component of a device affecting its performance. The principle of operation and a schematic energy level diagram for the materials used in the photoelectrochemical cells are presented. The device makes use of ITO films, TiO2 films, PVC-LiClO4 and graphite films as photoanode, photovoltaic material, solid electrolyte and counter electrode, respectively. The device shows rectification. The J(sc) and V-oc obtained at 100 MW cm(-2) were 0.95 mu Acm(-2) and 180 mV, respectively. (c) 2006 Elsevier B.V. All rights reserved.