Effect of citric acid (CA) on microstructure and photoelectrochemical properties of WO3 films prepared by the polymeric precursor method was investigated. The obtained materials were characterized by means of X-ray diffraction (XRD), field-emission scanning electron microscopy (FESEM), and high-resolution transmission electron microscopy (HRTEM). The results showed that samples prepared with adding different amounts of citric acid had a pure phase of cubic. The addition of citric acid could significantly increase the particle size and change the surface of WO3 films. The photoelectrochemical measurements were performed using a standard three-electrode system cell. The films prepared from mass ratios of CA/PEG (R = 0, 0.2, 0.4, 0.6 and 1) showed 1.0, 1.4, 1.7, 2.1 and 0.9 mA cm(-2) at 1.2 V under illumination with a 500 W xenon lamp (I-0 = 100 mW/cm(2)), respectively. (C) 2010 Elsevier B.V. All rights reserved.