Ordered-structure multilayer thin films were prepared on quartz substrates by the electrostatic self-assembly method. The UV-Vis-NIR spectrophotometer and the atomic force microscope (AFM) were used to characterize the films. The results indicated that order structure nanoporous TiO2 thin films showed high photocatalytic activity, and that the photocatalytic activity of heat-treated thin film was higher than that of UV irradiated film.