Hexagonal and cubic mesoporous TiO2 materials were synthesized via a sol-gel route modified by evaporation–induced self–assembly process with different templates. XRD and TEM results confirmed that the mesoporous films were highly organized. Furthermore, the hexagonal mesoporous TiO2 films were formed in the P123-templated films, whereas the cubic structure ones were found in the F127-templated films. Both the hexagonal and cubic mesoporous films showed photocatalytic activity in decomposing methyl orange solution under UV region, among which the cubic mesostructure presented superior potocatalytic activity because of larger surface area, more open framework and less obstructed diffusion paths of guest molecules.