Heteroarm H-shaped terpolymers, (polystyrene)(poly(methyl methacrylate))poly(tert-butyl acrylate)-(polystyrene)(poly(methyl methaerylate)), (PS)(PMMA)-PtBA-(PMMA)(PS), and, (PS)(PMMA)-poly(ethylene glycol)(PEG)-(PMMA)(PS), through click reaction strategy between PS-PMMA copolymer (as side chains) with an alkyne functional group at the junction point and diazide end-functionalized PtBA or PEG (as a main chain). PS-PMMA with alkyne functional group was prepared by sequential living radical polymerizations such as the nitroxide mediated (NMP) and the metal mediated-living radical polymerization (ATRP) routes. The obtained H-shaped polymers were characterized by using H-1-NMR, GPC, DSC, and AFM measurements. (c) 2006 Wiley Periodicals, Inc.