BACKGROUND: Photocatalytic water splitting is an attractive alternative for hydrogen generation because it is considered a clean and environment-friendly process. TiO2 semiconductor has been widely used in photocatalysis, however, its efficiency is limited due to the high recombination of the charge carriers. Many methods have been proposed to enhance TiO2 photoactivity, including modification with nonmetal ions and coupling with other semiconductor oxides. In this present work a series of CuO/TF photocatalysts with different CuO content were synthesized by impregnation of fluorinated TiO2 (TF) powder. These materials were characterized by several techniques and were studied in the hydrogen production reaction from a methanol/water solution under UV irradiation. RESULTS: The impregnation of the TF powder with Cu(NO3)(2)center dot H2O leads to the generation of crystalline and mesoporous materials and the existence of copper in the form of CuO. HRTEM results indicated the formation of heterojunctions between TiO2 and CuO phases. CuO(1.0)/TF photocatalyst was four times more active than TiO2 and fluorinated TiO2 support. CONCLUSIONS: The coexistence of fluoride and CuO species on TiO2 improves the photocatalytic properties of the semiconductor and the reduction of the H+ ions to H-2 is considerably better than that achieved with TiO2, TF and CuO/TiO2 materials. (C) 2017 Society of Chemical Industry.