In this study, TiO2 photocatalysts with nickel sulfide cocatalyst are prepared by loading nickel sulfide on TiO2 with solvothermal synthesis approach. The materials were prepared by glycol solvothermal method using anatase, nickel nitrate, thiourea as precursor. The prepared catalysts were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), ultraviolet visible diffuse reflectance spectroscopy (UV-vis DRS), and X-ray photoelectron spectroscopy (XPS). This is the first time to report that NiS is used as a cocatalyst with TiO2 for the photocatalytic production of H-2. The results revealed that the structure and the amount of the cocatalyst loaded on TiO2 play important roles in the photocatalytic activity of NiS/TiO2 composite. The maximum evolution of H-2 was obtained when NiS had hexagonal structure with content in the composite of 7 at% in relation to TiO2. The rate of H-2 evolution was increased up to about 30 times than that of TiO2 alone. Copyright (C) 2012, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.