A series of organic–inorganic hybrid materials have been prepared by copolymerizing styrene and alkoxysilane-methacrylate via the sol–gel process. The alkoxysilane-containing copolymer precursors were synthesized by free-radical copolymerization of styrene with an alkoxysilane-containing monomer, methacrylic acid 3-(trimethoxysilyl)propyl ester (MAMSE), at several feeds. The copolymer precursors were then hydrolyzed and condensed to generate PS–SiO 2 hybrid sol–gel materials. The hybrid copolymers possess excellent optical transparency and a nanoscale microphase separation. The copolymer precursors and their hybrid copolymers were characterized by FT-IR spectra, 1H NMR spectra, DSC, and TGA thermograms. Chemical structural effect on the morphology and thermal properties was investigated with SEM, mapping photographs, and high-resolution solid state 13C and 29Si NMR spectra. It was found that compatibility between copolymer and silica mainly comes from incorporating the polymer with silica covalently. Moreover, MAMSE could be hydrolyzed to methacrylic acid and ester-interchanged to silyl methacrylate during heat treatment. This also enhances the compatibility between the copolymer and silica. The thermal properties of the PS–SiO 2 hybrid copolymers are improved as silica content increase. However, the presence of silyl ester groups, which were formed during heat treatment, would reduce the thermal stability of the hybrid copolymers.