In the present research, random copolymers based on triethoxyvinylsilane (TEVS) and styrene (St) are synthesized and structurally characterized. According to the reactivity ratios of the monomers determined by infrared analysis; St tends to form blocks whilst TEVS is expected to be incorporated as isolated units. A sample of poly(styrene-co-triethoxyvinylsilane) synthesized at low conversion using a monomer feeding ratio St:TEVS of 2:3 was used as macrosilane in the synthesis of polystyrene-g-silica particles. The grafting reaction was confirmed by infrared spectroscopy, thermogravimetric analysis and by the evaluation of the morphological characteristics of the hybrid particles. (C) 2011 Elsevier B.V. All rights reserved.