Nanostructured titania film was synthesized using nonionic triblock copolymer P123 as surfactant template removed by ethanol extraction followed by calcination at different temperatures. The results of SAXRD indicate that the mesostructures of the films are not damaged until the calcination temperature as high to 450 degreesC. The results of TG/DSC, UV-visible and Raman spectra analyses provide the evidences for anatase phase to occur at 400 degreesC and above. The results of TEM and N-2 adsorption and desorption measures indicate that, with temperature increasing from 350 to 500 degreesC, anatase nanocrystal sizes and pore diameter increase, while the calculated BET surface area decreases. The photocatalytic activity of the films was characterized by the degradation test of methylene blue, and the results show that it depends on both the specific surface area and the crystallinity of nanostructured titania film.