Sulfur-doped titania thin films with cubic mesostructures were prepared by dip coating via the evaporation induced self-assembly route. The effect of sulfur doping on structure, morphology, porosity, optical properties, and photocatalytic activity of the mesoporous films was studied. Compared to undoped titania films, the S-doped films showed better long-range ordering, bigger pore size, higher porosity, less shrinkage of the structure during calcination, a red-shift of the band gap, and a more hydrophilic surface. These characteristics led to an improved photocatalytic activity when the S-doped and undoped titania films were tested for degradation of methylene blue in aqueous solutions under the irradiation of 1 sun from a solar simulator. The photocatalytic activity of the sulfur doped titania film was stable during three consecutive experiments under solar light irradiation, confirming the mechanical stability and reusability of the doped nanostructured thin film photocatalysts.