Crystalline titania films were prepared on the flexible polyimide (Kapton) substrates using the successive ionic layer adsorption and reaction (SILAR) technique modified with mixed organic amine template agents at room temperature. The titania film with the organic amine template agents presents orderly stacked morphology with cross linked V-shaped strips, and it composes of mainly anatase and minor rutile phases with N doping. Structural and morphology analysis indicates that there includes two parallel deposition growth processes: One is adsorption of the template agents and reaction with Ti 4+ ions on the constraint region; and the other is a normal SILAR process of including the adsorption of Ti 4+ ions and reaction with hydroxyl groups. The organic amine templates and their specific adsorption induce and direct the crystallization of the titania films. Crystal structure of the titania film was confirmed by its excellent photo catalytic property of the films, detected by the degradation test of MB.