This study examined hydrogen production over Cu-TiO2 photocatalysts containing CuxO, a conducting component. Nanometer particles of 0.1 mol% Cu-TiO2 were produced using the conventional sol-gel method; they were treated at 500 and 800 ℃ to obtain anatase and rutile structures, respectively. The CuO (d002 and d111 plane) peaks at 2θ values of 35.50º and 38.73º, respectively, appeared in the Cu-TiO2 sample treated at 800 ℃. The sizes of the pure TiO2 and Cu-TiO2 particles increased with the treatment temperature, while their surface areas decreased. The resulting Cu-TiO2 particles absorbed all wavelengths from 200 to 800 nm, unlike pure TiO2, which only absorbs wavelengths below 380 nm. X-ray photon spectroscopy (XPS) confirmed that the Cu2O and CuO components were dominant in the Cu-TiO2 photocatalysts treated at 500 and 800 ℃, respectively. The Ti 2p bands in the Cu-TiO2 samples were shifted to lower binding energies, which were assigned to Ti3+, relative to that of pure TiO2; the shift was the greater in the rutile structure than in the anatase form. The measured full widths at half maximum (FWHM) of the Ti 2p and Cu 2p peaks were larger in the rutile structure than in the anatase structure for both TiO2 and Cu-TiO2. The H2 production from methanol photodecomposition was greater over the rutile structure than over the anatase structure of TiO2. Moreover, the amount of hydrogen was enhanced over Cu-TiO2 compared to that over pure TiO2; the production reached 16,520 μmole after 24 h over rutile Cu-TiO2.