Two samples of ABCD 4-miktoarm star quarterpolymer with A = polystyrene (PS), B = poly(epsilon-caprolactone) (PCL), C = poly(methyl methacrylate) (PMMA) or poly(tert-butyl acrylate) (PtBA), and D = poly(ethylene glycol) (PEG) were prepared using click reaction strategy (Cu(I)-catalyzed Huisgen [3 + 2] reaction). Thus, first, predefined block copolymers of different polymerization routes, PS-b-PCL with azide and PMMA-b-PEG and PtBA-b-PEG copolymers with alkyne functionality, were synthesized and then these blocks were combined together in the presence of Cu(I)/N,N,N',N '',N ''-pentamethyldiethylenetriamine as a catalyst in DMF at room temperature to give the target 4-miktoarm star quarterpolymers. The obtained miktoarm star quarter polymers were characterized by GPC, NMR, and DSC measurements. (C) 2008 Wiley Periodicals, Inc.