A series of metal ion (M= Cr, Ni, Cu, Nb) and nitrogen co-doped TiO2 with high hydrogen production by photocatalytic water splitting were prepared by microwave-assisted hydrothermal method using titanium sulfate as precursor in the presence of urea. The catalysts were characterized by powder X-ray diffraction (XRD), Transmission Electron Microscopy (TEM), X-ray photoelectron spectroscopy analysis (XPS), N-2 sorption and Ultraviolet-visible spectroscopy (UV-vis). The photocatalytic water splitting was investigated in the presence of methanol as sacrificial hole scavengers under UV light irradiation and visible light irradiation. The rate of H-2 evolution was significantly changed with the variation of doped metal atoms, and their doping concentrations. Our results shows that the Cu/N co-doped TiO2 catalyst prepared by microwave-assisted hydrothermal exhibited the highest photoactivity, with a rate of H-2 production of 27.4 mmol g(-1) h(-1) under UV light irradiation and 283 mu mol g(-1) h(-1) under visible light irradiation. (C) 2015 Elsevier B.V. All rights reserved.