The uniform and transparent nano-crystalline thin films of pure and co-doped with Fe3+/Sn4+ titanium dioxide photo-catalysts were prepared via sol-gel dip-coating process, and were loaded firmly on the surface of glass substrates. The structure and surface morphology of films were characterized by X-ray diffraction (XRD) and atomic force microscopy (AFM). In particular, the photo-catalytic activity of films was measured by ultraviolet-visible (UV-VIS) spectrophotometer. Methyl orange was used as a model compound to study the photo-catalytic activity of films. The effects of the concentrations of doping ions and the number of layers on photo-catalytic degradation of methyl orange solutions were investigated. Experimental results showed clearly that the co-doping of iron and tin ions exhibited a synergistic effect, which increased significantly the photo-catalytic activity of titanium dioxide. Especially, the photo-catalytic activity of nano-crystalline titanium dioxide thin films co-doped with 0.1 mol%Fe3+ and 11.41mol%Sn4+ was 2.0 times higher than that of those un-doped for photo-degradation of methyl orange solutions under the 125W self-ballasted fluorescent high-pressure mercury lamp irradiation.