A new method to produce high-purity hydrogen using photoelectrocatalytic reactions is studied. This integrated process uses solar energy and the Gibbs free energy of oxidation of organic wastes to help reducing the energy consumption of water electrolysis. The method diminishes the thermodynamic potential to 0.77V and practical voltages to ca. 1.2V, due to an electrocatalytic reaction in the presence of iron ions. The anolyte is illuminated, and separated from the catholyte by a proton exchange membrane. The process oxidizes water pollutants and avoids the anodic corrosion of a stainless steel anode, but not every sacrificial substance has a positive effect on it. (c) 2004 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.