This article describes the synthesis and characterization of [polystyreneb-poly(2-vinylpyridine)](n) star-block copolymers with the poly(2-vinylpyridine) blocks at the periphery. A two-step living anionic polymerization method was used. Firstly, oligo(styryl)lithium grafted poly(divinylbenzene) cores were used as multifunctional initiators to initiate living anionic polymerization of styrene in benzene at room temperature. Secondly, vinylpyridine was polymerized at the periphery of these living (polystyrene), stars in tetrahydrofuran at -78 degrees C. The resulting copolymers were characterized using size exclusion chromatography, multiangle laser light scattering, H-1 NMR, elemental analysis, and intrinsic viscosity measurements. (C) 2007 Wiley Periodicals, Inc.