The synthesis of organic /inorganic hybrid materials was conducted by atom transfer radical polymerization (ATRP) of styrene and methyl methacrylate (MMA) from the surface of silica colloids, Colloidal initiators were prepared, by the functionalization of silica nanoparticles with (3-(2-bromoisobutyryl)propyl) dimethylethoxysilane (BIDS). Well-defined polymer chains were grown from the nanoparticle surfaces to yield individual particles composed of a silica core and a well-defined outer polystyrene (PS) or poly(methyl methacrylate) (PMMA) layer. Fourier transform infrared (FTIR) and solid state C-13 and Si-29- NMR spectroscopy confirmed the successful modification of nanosilica surfaces. Subsequent grafting of polymers on silica surfaces by ATRP was also performed with success based on FTIR and NMR data. Scanning electron microscopy (SEM) and silicon mapping showed both hybrid materials were homogeneous dispersion systems. Energy dispersive X-ray spectrometer (EDS) analysis indicated that the BIDS initiator was covalently attached on surfaces of silica nanoparticles and ATRP of styrene and MMA were accomplished. Thermogravimetric analysis (TGA) results displayed higher thermal stabilities for both nanohybrids in comparison with the linear-type vinyl polymers. Contact angle measurements revealed the nanomaterials character for both silica-based hybrid materials. (C) 2008 Wiley Periodicals, Inc.