A WO3/TiO2 composite film was in-situ prepared in tungstate electrolyte and characterized by Electron microscopy, X-ray diffraction, UV-Vis spectrophotometer and Photoluminescence. The oxide film consists of mixture phases of anatase and rutile, showing porous structures and metallurgical bond with substrate. With the incorporation of WO3 into TiO2, the optical absorption edge of TiO2 film was shifted to longer wavelength slightly and the separation between electrons and holes was promoted effectively. WO3/TiO2 composite film with increased photo quantum efficiency will be promising in the treatment of environmental pollutants. Crown Copyright (C) 2010 Published by Elsevier B.V. All rights reserved.