Aerogels are highly porous materials with potential application in thermal super-insulators for smart energy devices. Until now, the commercialization of silica-based aerogels has been restricted due to their brittle nature, and this drawback needs to be overcome by the improvement in the mechanical properties. Therefore, for the first time, the silane-based precursor triethoxy(1-phenylethenyl)silane (TPS) was introduced to synthesize the hybrid organic-inorganic aerogels. The simple, fast, and cost-effective free radical polymerization method was adopted to prepare TPS precursor. In present work, the tetraethylorthosilicate and TPS were introduced together at different molar ratios followed by hydrolysis-condensation and supercritical CO2 drying to achieve hybrid aerogels. The remarkable increase in the mechanical strength and hydrophobicity was found in the phenyl/vinyl hybridized aerogels compared with pristine silica aerogels. This facile synthesis approach provides new method to decorate the organic-inorganic hybrid aerogels.