Nanocomposite thin film containing TiO2nanoparticles in polymethyl methacrylate (PMMA) is a new class of potential materials for optoelectronic applications. Among the various processing techniques for these nanocomposites, in situ sol−gel process is well known to be versatile as it enables control of the inorganic-organic interaction at various molecular, nanometer and micrometer scales. However, the resulting TiO2phase is largely amorphous, as a consequence of the relatively low processing temperatures. Therefore, the current research is aimed at enhancing the nanocrystallinity of TiO2nanoparticles in nanocomposites. For this purpose, pre-hydrothermal treatment was carried on the inorganic sols. The nanocrystallinity degree of the resulting TiO2nanoparticles was studied by XRD and FTIR. The studies showed that the nanocrystallinity of TiO2nanoparticles synthesized from the inorganic sol can be enhanced significantly by the pre-hydrothermal treatment, as a result of the completion of hydrolysis stage during sol-gel process.