The films of TiO₂/ITO, ZrO₂/ITO, TiO₂-Zr/ITO and TiO₂/ZrO₂/ITO were prepared by ion-beam sputtering, all of which were also surface-sensitized with Rup₂O (p＝1,10-phenanthroline, O＝(3,4,5-tri- fluorophenyl) imidazo [5,6-f] phenanthroline) by using the rolling coat method. The physical parameters and energy levels of TiO₂-based and Rup₂O modified TiO₂-based films were ascertained by SPS and EFISPS. Because of the electron transitions between Ru 4d level and ligand levels (p₁^* and p₂^*), there were SPS peaks generated in Rup₂O modified films in the spectral wavelength range from 400 nm to 600 nm. The SPS intensity ratios between each of the SPS peak at 400～600 nm and that at 350 nm were different for different energy levels in the TiO₂-based films. The existence of Zr^4＋ doping level in TiO₂-Zr forbidden bands makes the decrease of the recombination of photo-induced carriers while leads to the increase of the number of photo-induced electrons. Moreover, the heterogeneous structure in TiO₂/ZrO₂ is beneficial to the electron transfer to surface of ITO, which can enhance the SPS response and photo-electron transformation efficiency.