Tungsten oxide (WO3) photoelectrodes with the surface tuned by Fe(III) for photoelectrochemical water splitting were successfully synthesized. Nanostructured WO3 films were prepared using doctor blade method, then a facile and economical deposition-annealing process was employed to fabricate Fe(III) modified WO3 films. The resulting composite's structural and optical properties were analyzed by SEM, EDX, XRD, UV-Vis spectrometry and XPS. The photoelectrochemical properties were evaluated by photocurrent density under 500 W Xe lamp with an intensity of 100 mW/cm(2). The Fe(III) modified WO3 electrode exhibited a larger photocurrent than the pure WO3 electrode. Significantly, the optimized Fe(III) modified WO3 film achieved the maximum photocurrent density of 1.18 mA/cm(2) at 0.8 V vs. Ag/AgCl in the 0.2 M Na2SO4.The enhanced photocurrent was attributed to the extension of the light response and the electron hole separation at the interface Fe(III)/WO3 which was confirmed by Mott-Schottky and electrochemical impedance spectroscopy. Copyright (c) 2012, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.