N-doped TiO2 effectively extends the light response range of TiO2 photocatalysts from the ultraviolet to the visible region; a p-n heterojunction would favor the separation of photogenerated electron-hole pairs, leading to high quantum efficiency, and consequently, enhanced photocatalysis. A Cu2O/N-TiO2 hybrid catalyst with p-n heterojunctions was newly prepared using a solvothermal and chemical reduction method. The hierarchical structure and valence state of copper of the Cu2O/N-TiO2 catalyst have been confirmed using X-ray diffraction, high resolution transmission electron microscopy, and X-ray photoelectron spectroscopy. The hybrid Cu2O/N-TiO2 catalyst demonstrated good photostability and excellent photocatalytic activity toward H-2 production, with a rate of 11 mu mol g(-1) h(-1) under visible light irradiation (> 400 nm) of a methanol aqueous solution. This offers an inexpensive and facile approach for potential efficient solar photon-driven H-2 production.