An efficient composite catalyst, CuO/CF/TiO2 (where CF represents catalytic grown carbon fiber and TiO2 is the commercial product P25), is prepared with a wet impregnation and calcination process and is applied in the photo stimulated catalytic water splitting. The modification of TiO2 with CuO, serving as the H-2 evolution cocatalyst, and carbon fiber, behaving as the electron transporter, enhances greatly the overall activity of the material. The activity of CuO/CF/TiO2 with 1 wt% CF is 45 times higher than that of TiO2 and 2 times higher than that of CuO/TiO2. CF and CuO play a synergistic role in decreasing the recombination rate of the photogenerated carriers in TiO2 bulk phase. The CF in the composite catalyst extends the reaction range, and makes the reaction proceeds on both the surface of CuO intimately contacting with TiO2 particles and the surfaces of the CuO particles which do not in contact with TiO2 but in contact with CF. Copyright (C) 2013, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.