A hybrid organic-inorganic material was prepared by surface initiated controlled/"living" radical polymerization (CRP) of styrene in the internal space of a MCM-41 silica. The inorganic precursor was synthesized, via sol-gel, using tetraethoxysilane and cetyltrimethylammonium bromide, in the presence of ammonia and ethanol to induce the formation of submicrometric spherical particles. After characterization by powder X-ray diffraction (XRD), transmission electron micrography (TEM), scanning electron micrography (SEM), N-2 adsorption and titration of the surface silanol groups, the mesoporous silica was functionalized through a 3-step grafting process, in order to link the nitroxide initiator to the inorganic matrix (TEMPO-MCM-41). The anchorage of the TEMPO-based initiator was checked by diffuse reflectance infrared spectroscopy (DRIFT-IR). Experimental data confirmed that the styrene polymerization occurred inside the MCM-41 channels system.