Cu-modified TiO2 photocatalysts (Cu/TiO2) were fabricated by electroless plating and wet impregnation methods. Photocatalytic activity for H-2 production over Cu/TiO2 by electroless plating method was higher than that over Cu/TiO2 by impregnation method. Characterization of Cu nanoparticles by HRTEM, STEM-EDX, XRD and XAFS was studied. As compared to the wet impregnation method, the electroless plating method resulted in the formation of Cu nanoparticles with small size and uniform distribution on the TiO2 surface, which caused the enhancement of H-2 production. XAFS measurement provided the evidences for the chemical state change of Cu species during the photocatalytic reaction. The process that Cu species varied from Cu2+ into Cu-0 via Cu1+ as the intermediate under photoirradiation is very important for the H-2 production, which indicates that the metallic Cu nanoparticles acted as the active sites and restrained the photogenerated charges recombination.