Hybrid inorganic/organic materials consisting of a poly(n-butyl acrylate)-b-poly(styrene) diblock copolymer anchored to silica particles were synthesized via 'grafting from' technique using a controlled/living free radical polymerization named stable free radical polymerization. XPS and FTIR analysis were used to control the effectiveness of the chemical modification of the silica particles. Thermal characterizations were performed by thermal gravimetric analysis (TGA) and by differential scattering calorimetry (DSC). The TGA permitted the determination of the quantity of grafted polymer and thus the grafting density; DSC was used to study the influence of the silica and blocks of the copolymer on their thermal behaviors. The glass transition temperature of the grafted copolymers was compared to these of free polymers or copolymers homologues. (C) 2004 Elsevier Ltd. All rights reserved.