Triethoxyvinylsilane–styrene and triethoxyvinylsilane–methyl methacrylate binary monomers were polymerized by chemical initiation or by γ-ray irradiation in the presence of silica gel, fire brick, quartz wool, and glass beads. The amount and composition of the polymers grafted to silicates were analyzed by using pyrolysis gas chromatography. When triethoxyvinylsilane alone was subjected to the reaction with silicates, condensation occurred irrespective of the initiating means, and the extent of the reaction was almost proportional to the specific surface area of the silicate. When binary monomer mixture was applied, incorporation of styrene or methyl methacrylate into the grafted polymer was observed whenever a monomer mixture of high styrene or methyl methacrylate content was submitted to the reaction. On each silicate, the relationship between the composition of polymer grafted on it and that of monomer showed a similar pattern in spite of the great difference of the specific surface area. Almost no participation of styrene or methyl methacrylate was observed when the silicate preirradiated in air or under vacuum was heated with the binary monomer mixture. It was concluded that triethoxyvinylsilane reacts with silicates by condensation and that some of the pendent vinyl groups on the silicates are incorporated into the copolymer with styrene or methyl methacrylate.