A series of star block copolymer consisting of poly(stearyl methacrylate) and poly(3-(trimethoxysilyl)propyl methacrylate) was synthesized via atom transfer radical polymerization technique. The resultant polymers were characterized by gel permeation chromatography and H-1 NMR. The copolymer can self-assemble into the aggregates in selective solvents, the resulting aggregates can be used as precursor to prepare hybrid nanomaterials conveniently via the hydrolysis reaction of -Si(OCH3)(3) groups and the condensation reaction of -Si(OH)(3) groups. Moreover, the effect of the star copolymer-solvent interaction on the aggregation behavior was also discussed. (C) 2008 Wiley Periodicals, Inc.