A novel polyimide (PI) hybrid nanocomposite containing polyhedral oligomeric silsesquioxane (POSS) had been prepared by copolymerization of octa(aminophenyl)silsesquioxane (OAP-POSS), 4,4’ -oxydianiline (ODA), and pyromellitic dianhydride (PMDA). The AO resistance of these POSS/PI hybrid films was tested in the ground-based AO simulation facility. Exposed and unexposed surfaces have been characterized by X-ray photoelectron spectroscopy and FTIR. The XPS data indicate that the carbon content of the near-surface region is decreased from 63.6 to 19.3 at% after AO exposure. The oxygen and silicon concentrations in the near-surface region increase after AO exposure. The data reveal the formation of a passive inorganic SiO2 layer on the POSS/PI hybrid films during the AO exposure, which serves as a protective barrier preventing further degradation of the underlying polymer with increased exposure to the AO flux. SEM images showed that the surface of the 10 wt% POSS/PI became much less rough than that of the pristine polyimide. The AO resistance of the POSS/PI hybrid films is up to several tenfold than that of the pristine polyimide.