In this study, preparation of Sn and Nb co-doped TiO2 dip-coated thin films on glazed porcelain substrates via sol–gel process have been investigated. The effects of co-doping content on the structural, optical, and photo-catalytic properties of applied thin films have been studied by X-ray diffraction (XRD), field emission SEM (FE-SEM), high resolution transmission electron microscopy (HR-TEM), and UV-Vis absorption spectroscopy. Surface chemical state of thin films was examined by atomic X-ray photoelectron spectroscopy (XPS). XRD results suggest that adding impurities has a great effect on the crystallinity and particle size of TiO2. Titania Rutile phase formation in thin film was promoted by Sn4+ addition but was inhibited by Nb5+ doping. The prepared co-doped TiO2 photo-catalyst films showed optical absorption edge in the visible light area and exhibited excellent photo-catalytic ability for degradation of methylene blue (MB) solution under solar irradiation. Comparison with undoped and Sn or Nb-doped TiO2, codoped TiO2 shows an obviously higher catalytic activity under solar irradiation.