Nanocrystalline titania porous films were prepared on ITO and glass substrates by polyethylene glycol（PEG）-assisted sol-gel method using Ti(C4H9COO)4 as precursor, ethanol as solvent and NH(C2H2OH)2 as chelating agent and PEG 2000as a template. When the amount of polyethylene glycol is within the range of 0～2. 0g/L ,. The characteristics and microstructure of films as well as the chemical and physical changes taken place during so-gel and heat treatments were analyzed by XRD, SEM and Emission spectra. The Cyclic voltammetry which measurements the films by illumination with a high pressure mercury lamp are employed to analyze photoelectrochemical property the porous titania thin films. The effects of precursor concentration and PEG 2000 contention the characteristic of films were discussed. The Cyclic voltammetry experiment under UV light irradiation indicated that the pores in the TiO2 thin films enhanced its photoelectrochemical activity; the size of the pores thin films obviously affected the photo-current exchanged rate of titania films.