A series of inorganic-organic thin films based on uniformly dispersed nanoparticles of polyoxometalates (POM) entrapped in polyacrylamide (PAM) matrix were prepared by ultrasonic method with different irradiation time. The microstructure,photochromic behavior and mechanism of the films were studied by transmission electron microscopy (TEM),ultraviolet-visible spectra (UV-VIS) and Fourier transform-infrared spectroscopy (FT-IR). The microstructure and photochromic properties of the hybrid thin films could be controlled by ultrasound. TEM image revealed that the average size of phosphotungstic acid (PWA) nanoparticles decreased from 20 to 10 nm with the ultrasound irradiation time from 30 to 60 min.After irradiated with ultraviolet light, the transparent films changed from colorless to blue and showed reversible photochromism.The hybrid film,with ultrasound irradiation for 60 min had higher photochromic efficiency and faster bleaching reaction than the one with ultrasound irradiation for 30 min.FT-IR spectra showed that the Keggin geometry of heteropolyoxometalate was still preserved inside the composites,and the interactions between polyanions and polymer matrix increased as the ultrasound time prolonged.It is suggested that the mechanism of the different photochromic properties for the inorganic-organic thin films is the variation of the microstructure and interfacial interactions induced by ultrasound. A series of inorganic-organic thin films based on attributable nanoparticles of polyoxometalates (POM) entrapped in polyacrylamide (PAM) matrix were prepared by ultrasonic method with different irradiation time. The microstructure, photochromic behavior and mechanism of the films were studied by transmission electron microscopy (TEM), ultraviolet-visible spectra (UV-VIS) and Fourier transform-infrared spectroscopy (FT-IR). The microstructure and photochromic properties of the hybrid thin films could be controlled by ultrasound. TEM image revealed that the average size of phosphotungstic acid (PWA) nanoparticles decreased from 20 to 10 nm with the ultrasound irradiation time from 30 to 60 min. After irradiated with ultraviolet light, the transparent films changed from colorless to blue and showed reversible photochromism. The hybrid film, with ultrasound irradiation for 60 min had higher photochromic efficiency and faster bleaching reaction than the one with ultrasound irradiation for 30 min. FT-IR spectra showed that the Keggin geometry of heteropolyoxometalate was still preserved inside the composites, and the interactions between polyanions and polymer matrix increased as the ultrasound time prolonged. It is suggested that the mechanism of the different photochromic properties for the inorganic -organic thin films is the variation of the microstructure and interfacial interactions induced by ultrasound.