TiO2 photocatalyst with deposited CuO (CuO-TiO2) was synthesized by the impregnation method using P25 (Degussa) as support, and exhibited high photocatalytic hydrogen generation activity from methanol/water solution. A substantial hydrogen evolution rate of 10.2 ml min(-1) (18,500 mu mol h(-1) g(catalyst)(-1)) was observed over this efficient CuO-TiO2 with optimal Cu content of 9.1 mol% from an aqueous solution containing 10 vol% methanol; this improved hydrogen generation rate is significantly higher than the reported Cu-containing TiO2, including some Pt and Pd loaded TiO2. Optimal Cu content of 9.1 mol% provided maximum active sites and allowed good light penetration in TiO2. Over this efficient CuO-TiO2, the hydrogen generation rate was accelerated by increasing the methanol concentration according to Freundlich adsorption isotherm. However, the photocatalytic hydrogen generation rate was suppressed under long time irradiation mainly due to accumulation of by-products, reduction of CuO and copper leaching, which requires further investigation. (C) 2009 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.