A bilayer WO3/Fe2O3 heterojunction photoelectrode was prepared with a new approach for photoelectrochemical reactions. WO3 was deposited onto an FTO conductive glass substrate via electrodeposition, followed by the deposition of an ultrathin Fe2O3 layer using the chemical bath deposition method. The presence of Fe2O3 layer improved the light absorption of WO3/Fe2O3 toward visible light region (red-shift). The addition of a thin layer of Fe2O3 on WO3 resulted in higher photocatalytic performance (two-fold improvement) compared to that of pristine WO3. In addition, the WO3/Fe2O3 photoelectrode also showed a positive photoresponse for methanol degradation. The photocurrent generation of the bilayer photoelectrode improved 1.6-fold with the addition of methanol as a sacrificial donor. (C) 2017 Elsevier Ltd. All rights reserved.