Abstract BACKGROUND Photocatalytic water splitting is an attractive alternative for hydrogen generation because it is considered a clean and environment‐friendly process. TiO 2 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 TiO 2 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 TiO 2 (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(NO 3 ) 2 •H 2 O 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 TiO 2 and CuO phases. CuO(1.0)/TF photocatalyst was four times more active than TiO 2 and fluorinated TiO 2 support. CONCLUSIONS The coexistence of fluoride and CuO species on TiO 2 improves the photocatalytic properties of the semiconductor and the reduction of the H + ions to H 2 is considerably better than that achieved with TiO 2 , TF and CuO/TiO 2 materials. © 2017 Society of Chemical Industry