Ordered mesoporous WO3-TiO2 composite films with different WO3 contents were prepared on the FTO glass as functional catalyst support material for direct methanol fuel cells. The introduction of WO3 reduced the titania phase transformation temperature and a part of anatase had transformed into rutile. With the 0.5 wt% of WO3, the mesoporous composite film had well-ordered mesostructure and the best mixed ratio of anatase and rutile, indicating the optimal performance of photoelectrochemical oxide of methanol. For the prepared ordered mesoporous Pt-WO3-TiO2 film electrodes, the photocatalytic activity in methanol oxidation was optimized at 0.5 wt% of WO3, whose photo-electrocatalytic activity was 3.6 times than that of a mesoporous TiO2 film without WO3, due to the electron hole separation efficiency and the special synergetic effects between Pt and holes under UV illumination. (C) 2013 Elsevier B.V. All rights reserved.