Two types of multiarm star block copolymers: (polystyrene)(m)-poly(divinylbenzene)-poly(methyl methacrylate)(n), (PS)(m),-polyDVB-(PMMA)(n) and (polystyrene)(m)-poly(divinylbenzene)-poly(tert-butyl acrylate)(k), (PS)(m)-polyDVB-(PtBA)(k) were successfully prepared via a combination of cross-linking and Diels-Alder click reactions based on "arm-first" methodology. For this purpose, multiarm star polymer with anthracene functionality as reactive periphery groups was prepared by a cross-linking reaction of divinyl benzene using a-anthracene end functionalized polystyrene (PSAnth) as a macroinitiator. Thus, obtained multiarm star polymer was then reacted with furan protected maleimide-end functionalized polymers: PMMA-MI or PtBA-MI at reflux temperature of toluene for 48 h resulting in the corresponding multiarm, star block copolymers via Diels-Alder click reaction. The multiarm star and multiarm star block copolymers were characterized by using H-1 NMR, SEC, Viscotek triple detection SEC (TD-SEC) and UV. (c) 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 178-187, 2009