Abstract: Taking polystyrene as template, TiO2 film thin with photonic crystal structure was prepared by sol-gel method to copy, and SEM, UV-vis spectrophotometer were employed to characterize the film structure. Dye-sensitization cell with N3 was assembled using the TiO2 as electrode, the absorption and reflection spectrum were drawed through full spectrum microspectrophotometer, and the volt-ampere characteristic was tested. The results show that TiO2 thin film with photonic crystal structure could be successfully obtained, which had ordered, large and arranged-periodical pores. The light absorption and photoelectric conversion properties of the TiO2 film were improved. The absorption intensity of the film increased after dye-sensitization in the visible region. Compared with ordinary TiO2 film with same thickness, the dye-sensitized cell assembled with the TiO2 film with photonic crystal structure had higher short-circuit current and open-circuit voltage, and the fill factor and cell efficiency were improved.