BiVO4 and Ag-doped BiVO4 were hydrothermal synthesized and characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction, Raman, X-ray photoelectron spectroscopy (XPS), UV-Vis diffusion reflectance spectroscopy and room-temperature photoluminescence spectra (PL) and photoelectron-chemical measurement. The structural and morphological characterizations reveal that the Ag species, existing as Ag4V2O7 phase, has a significant influence on the morphology and induces a progressive conversion of monoclinic to tetragonal BiVO4. The as-prepared Ag-doped BiVO4 composites exhibit much higher photocatalytic activities for H-2 evolution from the ethanol-triethylamine aqueous solution as compared to bare BiVO4. The 4 wt.% Ag-doped BiVO4 possesses the highest photocatalytic activity, and hydrogen production rate of 205 mu mol h(-1).g(-1) can be obtained. The highly improved performance can be attributed to the efficient charge transfer and separation from the coupling effect of Ag4V2O7 semiconductor and monoclinic/tetragonal heterostructured BiVO4 system. Copyright (C) 2015, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.