Electrical power generated by a photovoltaic cell (PVC) was supplied to diluted industrial wastewater in a mechanically mixed and sealed stainless-steel reactor for hydrogen gas production. Three different electrodes, graphite, stainless steel and aluminum rods were used for comparison. Protons released from decomposition of organic compounds and electrons provided by the DC current reacted to form hydrogen gas. The highest cumulative hydrogen gas formation (CHF) was obtained with the aluminum electrode (120 L in 8 days) and the lowest was with the graphite electrode (4 L). Hydrogen gas production from wastewater was 2.4 times higher than that produced from water when aluminum electrodes were used. TOC content of wastewater was reduced from 2400 to 1700 mg L(-1) with nearly 29% TOC removal within 6 days. CHF from wastewater was 76 L within 18 days with the stainless-steel electrodes while CHF from water was only 9.5 L. Fermentative hydrogen gas production from wastewater was negligible in the absence PVC. Energy conversion efficiency for hydrogen gas production (hydrogen energy/electric energy) was found to be 74% with the aluminum electrodes. Copyright (C) 2010, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.