In this study, Au/TiO2 samples with different exposed facets ({100}, {100/111}, and {111}) of Au were employed as catalysts for the examination of facet-dependent catalytic activity toward photocatalytic hydrogen evolution from water. By photosensitized using Eosin Y as antenna molecule, Au/TiO2 series photocatalysts exhibited different photocatalytic hydrogen evolution performances under visible light irradiation. Au{111}/TiO2 photocatalyst presented the highest photocatalytic hydrogen generation activity among Au/TiO2 series samples. As evidenced by photoluminescence spectra, photocurrent, electrochemical impedance spectra, and Mott-Schottky characterizations, the difference in photocatalytic activities resulted from the different electron transfer rates from the conduction band of TiO2 to Au nanoparticles. Au nanoparticles with exposed {111} facets were more effective in trapping electrons due to their higher Fermi level. In addition, the apparent activation energy of Au{111}/TiO2 sample was the lowest, resulted from the biggest uncoordinated numbers of Au atoms on Au{111} nanoparticles, which was favor in forming the hydrogen-metal bond. This study discloses the facet-dependent effect of noble-metal cocatalyst on semiconductor photocatalysts in photocatalytic water reduction, and will give an insight into design and synthesis of high-efficient noble metal/ semiconductor hybrid photocatalysts. Copyright (C) 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.