The heterojunction films of WO3/TiO2 were prepared by liquid phase deposition (LPD) method via two-step processes. The scanning electron microscopy, X-ray diffraction and X-ray photoelectron spectroscopic analysis indicated that flower-like WO3 film was successfully deposited on TiO2 film with the LPD processes. The TiO2 film provided an excellent platform for WO3 deposition while WO3 obviously expanded the absorption of TiO2 film to visible light. As the result, the heterojunction film of WO3/TiO2 exhibited higher photocurrent response to visible light illumination than pure TiO2 or WO3 film. The photoelectrocatalytic (PEC) activity of WO3/TiO2 film was evaluated by degrading Rhodamin B (RhB) and 4-chlorophenol (4-CP) under visible light irradiation. The results showed that the LPD WO3/TiO2 film possessed high PEC activity for efficient removal of various refractory organic pollutants. (C) 2014 Elsevier Ltd. All rights reserved.