Photocatalysts CuS/TiO2 for hydrogen production were synthesized by hydrothermal method at high temperature and characterized by XRD, UV-visible DRS, XPS, EDX, SEM and TEM. When TiO2 was loaded with CuS, it showed photocatalytic activities for water decomposition to hydrogen in methanol aqueous solution under 500 W Xe lamp. Among the photocatalysts with various compositions, the one with 1 wt% CuS-loaded TiO2 showed the maximum photocatalytic activity for water splitting, which indicated CuS could improve the separation ratio of photoexcited electrons and holes. What's more, the amounts of the produced hydrogen was about 570 mu mol h(-1), which had exceeded pure titania (P25) 32 times. In the present paper, it is proven that CuS can act as an effective co-catalyst to enhance the photocatalytic H-2 production activity of TiO2. Copyright (C) 2013, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.