Polystyrene/silica, polystyrene–butylacrylate/silica, silylated polystyrene/silica, and silylated polystyrene–butylacrylate/silica hybrid composites were synthesized by the sol–gel method in tetrahydrofuran using HCl as catalyst and tetraethylorthosilicate as the silica precursor. The polymers were characterized by fourier transform infrared (FTIR), nuclear magnetic resonance, and gel permeation chromatography. The sol–gel mixtures were cast on glass plates and dried in air at 30°C for 72 h. The composites were characterized by FTIR, thermogravimetric analysis, differential scanning calorimetry, and scanning electron microscopy analysis. Silica (12.8%) could be incorporated within the silylated polystyrene–butylacrylate matrix while retaining optical transparency. These composites showed better thermal stability and water resistance in comparison to the individual polymers.