TiO2/ITO, TiO2-Zn/ITO and TiO2/ZnO/ITO films were prepared by ion-beamsputtering, and then further surface-sensitized with the Ru(phen)2(PIBH) complex (Rup2P) of Rup2P/TiO2/ITO, Rup2P/TiO2-Zn/ITO, and Rup2P/TiO2/ZnO/ITOby the spin-coating method. Surface photovoltage spectra (SPS) of the films revealed that SPS responses were present at 400-600 nm after surface-sensitization and the SPS intensity ratios between the peaks at 400-600 nm and 350 nm were different because of the different energy band structures in the TiO2-based films. The physical parameters and energy band structures of TiO2-based and Rup2P modified TiO2-based films were determined by electric field induced surface photovoltage spectroscopy (EFISPS). We found that the 400-600 nm SPS peaks of the Rup2P modified films came from the Ru 4d to phen π*1 and PIBH π*2 electron transitions. The Zn2+ doping level in TiO2-Zn benefits the injection of photogenerated electrons from the ligand levels to the conduction band. The TiO2/ZnO heterostructure favors electron transfer to the surface of ITO, which can enhance the SPS response in the visible light region (400-600 nm) as well as the photoelectron transformation efficiency.