TiO2 sol-gel composite films with dropping molybdenumphosphoric acid (PMoA) have been prepared by sol-gel method. The structure and constitute of composite thin films were studied with Fourier transforms infrared spectroscopy (FT-IR), atomic force microscopy (AFM), and X-ray diffraction (XRD) patterns, respectively. The photochromic behavior and mechanism of composite thin films were inves-tigated with ultraviolet-visible spectra (UV-vis) and electron spin resonance (ESR). FT-IR results showed that the Keggin geometry of PMoA was still preserved inside PMoA/TiO2 composite thin films, and a charge transfer bridge was built at the interface of PMoA and TiO2 through the Mo-O-Ti bond. Surface topography of the composite film showed obvious changes before/after adding PMoA, and the surface topography of composite films showed obvious changes before/after irradiating as well. Composite thin film had reversible photochromic properties. Irradiated with UV light, transparent films changed from colorless to blue and they can bleach completely with ambient air in the dark. ESR re-sults showed that TiO2 were excitated by UV light to produce electrons, which deoxidized PMoA to produce heteropolyblues. The photochromic process of PMoA/TiO2 system was carried through elec-tron transfer mechanism.