Photocatalytic hydrogen evolution is a potential route for converting inexhaustible solar energy into available clean chemical energy. Herein, highly efficient and stable Cu-2(OH)(2)CO3/TiO2 photocatalysts for hydrogen generation are prepared by incorporating Cu-2(OH)(2)CO3 clusters onto the surface of TiO2 through a facile precipitation method. The obtained Cu-2(OH)(2)CO3/TiO2 photocatalyst with optimal Cu-2(OH)(2)CO3 content of 0.5 mol% shows an outstanding photocatalytic H-2-production rate of 6713 mu mol h(-1) g(-1) (with apparent quantum efficiency of 15.4% at 365 nm), which is comparable to the excellent Pt/TiO2 photocatalyst and more efficient than other copper specie modified TiO2 photocatalyst. The formation of Cu-2(OH)(2)CO3/Cu+/Cu-0 clusters essentially contribute to the enhanced H-2-production activity by reducing the over-potential of water reduction and promoting the transfer of photogenerated electrons from the conduction band of TiO2 to the Cu-2(OH)(2)CO3/Cu+/Cu-0 clusters. A high stability of the Cu-2(OH)(2)CO3/TiO2 photocatalyst is achieved due to the re-oxidation process of Cu+/Cu-0 to Cu-2(OH)(2)CO3 and structure confinement of Cu-2(OH)(2)CO3 clusters in the mesopores of TiO2. This work brings in new insight in developing low-cost noble-metal-free photocatalytic system for solar-to-fuel conversion. (C) 2016 Elsevier B.V. All rights reserved.