In this paper, PMMA-silica hybrid thin films were synthesized via a versatile non-hydrolytic sol-gel (NHSG) process. The resulted hybrid films have been investigated by FT-IR, scanning electron microscopy (SEM), UV/vis spectrometry, atomic force microscopy (AFM), differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The hybrid films show higher glass transition temperatures (T.) according to the DSC results, which indicate the strong interfacial interactions between polymer moiety and silica particles. The inorganic particles are well dispersed in PMMA matrices seen from SEM image. TGA results demonstrate that the thermal decomposition temperature of the hybrid films increase from 365.1 degrees C for neat PMMA to 385.8 degrees C. In comparison with the samples prepared by traditional sol-gel (SG) route, these hybrids exhibit higher optical transparency and better thermal stability and their structural differences between the hybrids synthesized by NHSG and SG are also studied. (c) 2007 Elsevier B.V. All rights reserved.