This study investigated the production of hydrogen over Cu (1, 5, 10 and 15 mol%)/TiO2 photocatalysts loaded with CuO, prepared by an impregnation method. The CuO (002 and 111 plane) peaks at 2 theta = 35.50 degrees and 38.73 degrees appeared with above 5 mol% loaded TiO2. The CuO component (Cu2p(3/2)) at 933.5-934eV was shown in the XPS band of the Cu/TiO2 photocatalysts, which increased in size with increasing amount of loaded Cu. All of Ti2p(3/2) bands for Cu/TiO2 appeared at 458.8eV, which were assigned to Ti4+, most likely due to pure TiO2. The measured full widths at half maximum (FWHM) of the Ti2p peaks for Cu/TiO2 were larger compared to that of pure TiO2; a larger FWHM implies a greater amount of less-oxidized metals. The ratios of metal-OH/metal-O in the O1s bands, which imply hydrophilicity, were increased in the Cu/TiO2 compared to pure TiO2. The production of H-2 from methanol/water photodecomposition was greater over the Cu/TiO2 photocatalysts than over the pure TiO2; the production reached 13,500 mu mol after 10 h over 10 mol% Cu/TiO2. (c) 2007 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.