Abstract: The research concerns in the preparation and TiO₂ assembly of mesoporous silica films at ambient pressure by sol-gel technique. First, the silicate sol was prepared with the procursor acitetraehoxysilane(TEOS) and cationic surfactant hexadecyl trimethyl ammonium bromide(CTAB) or amphiphilic triblock copolymer（EO₂₀PO₇₀EO₂₀）as template dissolved in ethanol and catalyzed by hydrochloric acid. Then the film was obtained by dip coating, and both XRD patterns and TEM image indicate that the films are highly ordered. Finally, the TiO₂ nanofiber was prepared by impregnating a mesoporous silica film with TiCl₄ followed by hydrolysis in air and calcination at high temperature in the oven. The prepared TiO₂nanofiber diameter is in the range of 50~300 nm and it was characterized by SEM. TiO₂ nanofibers can’t be formed on film containting template or bare substrate. TiO₂ nanofiber morphology can be varied by controlling the pore size of the mesoporous silica film. TiO₂ nanofiber has anatase phase after heating at200~600 ℃and its crystallization increases with calcination temperature increasing.