The effects of postthermal treatment and irradiation time on the structure and thermal stability of TiO2/polyacrylate nanocomposites by a sol-gel process in reverse micelles and subsequent rapid photopolymerization were investigated, and the hybrid films were characterized by thermal gravimetry analysis (TGA), X-ray photoelectron spectrum (XPS), and atomic force microscopy (AFM).XPS data suggested that the prolongation of irradiation time and the postthermal treatment promoted titania formation, with the former affecting more remarkably. TGA data showed that TiO2-hybrid films could upgrade the decomposition onset temperature (Tonset) as well as the temperature at which there is a maximum mass loss rate (Tmax). AFM data demonstrated that the inorganic titania particles with a mean diameter of 25.26-28.84 nm were homogeneously distributed in the organic matrix.