Mesoporous tungsten trioxide (DDA-WO3) was prepared using tungstic acid (H2WO4) as a tungsten precursor, dodecylamine (DDA) as a surfactant template which has structure guiding function. The specific surface area (57.3 m2·g-1) of DDA-WO3 was 2.35 times of 24.5 m2·g-1for WO3 (H2WO4-WO3) prepared without DDA. X-ray diffraction (XRD) result of the DDA-WO3 calcined at 400 ℃ indicates that a crystalline framework with disordered arrangement of pores. The crystallinity of DDA-WO3 calcined at 400~550 ℃ is higher than each of H2WO4-WO3. DDA-WO3/FTO (SnO2∶F) calcined at 400 ℃ generates photoanodic current density of 0.18 mA·cm-2 at 1.0 V versus Ag/AgCl, which is about 3 times higher than that of the H2WO4-WO3/FTO(0.06 mA·cm-2). The enhanced photoelectrochemical (PEC) performance of DDA-WO3/FTO suggests that the higher specific surface area of mesoporous structure is a dominant factor for the PEC performance rather than insufficient crystallinity. DDA-WO3/FTO calcined at 500 ℃ still exhibites excellent PEC performance than H2WO4-WO3/FTO due to higher crystallinity, although the degradation of the mesostructure at higher temperature.