The nanocrystalline S doped titanium dioxide films were successfully prepared by the improved sol-gel process. Here TiO(C4H9O)(4) and CS(NH2)(2) were used as precursors of titania and sulfur, respectively. The as-prepared specimens were characterized using x-ray diffraction (XRD), x-ray energy dispersive spectroscopy (EDS), high-resolution field emission scanning electron microscopy (FE-SEM), Brunauer-Emmett-Teller (BET) surface area, and ultraviolet-visible diffuse reflectance spectroscopy. The photocatalytic activities of the films were evaluated by degradation of organic dyes in aqueous solution. The results of XRD, FE-SEM, and BET analyses indicated that the TiO2 films were composed of nanoparticles. S doping could obviously not only suppress the formation of brookite phase but also inhibit the transformation of anatase to rutile at high temperature. Compared with pure TiO2 film, S doped TiO2 film exhibited excellent photocatalytic activity. It is believed that the surface microstructure of the modified films is responsible for improving the photocatalytic activity.