Azide end-functionalized polyhedral oligomeric silsesquioxane (POSS-N-3) was incorporated into the periphery of well-defined alkyne-polystyrene(50)-poly(divinyl benzene) (alkyne-PS50-polyDVB) and alkyne-poly(tert-butyl acrylate)(43)-poly(divinyl benzene) (alkyne-PtBA(43)-polyDVB) multiarm star polymers via highly efficient azide-alkyne click reaction, resulting in POSS-PS50-polyDVB and POSS-PtBA(43)-polyDVB multiarm star block copolymers respectively, in the solution of tetrahydrofuran/N,N-dimethyl formamide, CuBr/N,N,N',N '',N ''-pentamethyldiethylenetriamine (PMDETA) at room temperature for 24 h. Linear precursors and star polymers obtained in this study were characterized H-1 NMR, gel permeation chromatography (GPC), and triple detection GPC (TD-GPC). Absolute molecular weight, hydrodynamic radius, and intrinsic viscosity ([eta]) values for all star polymers were determined by TD-GPC. (C) 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 4835-4841, 2010