Well-defined linear furan-protected maleimide-terminated poly(ethylene glycol) (PEG-MI), tetramethylpiperidine-1-oxyl-terminated poly(epsilon-caprolactone) (PCL-TEMPO), and azide-terminated polystyrene (PS-N(3)) or -poly(N-butyl oxanorbornene imide) (PONB-N(3)) were ligated to an orthogonally functionalized core (1) in a two-step reaction mode through triple click reactions. In a first step, DielsAlder click reaction of PEG-MI with 1 was performed in toluene at 110 degrees C for 24 h to afford alpha-alkyne-alpha-bromide-terminated PEG (PEG-alkyne/Br). As a second step, this precursor was subsequently ligated with the PCL-TEMPO and PS-N(3) or PONB-N(3) in N,N-dimethylformamide at room temperature for 12 h catalyzed by Cu(0)/Cu(I) through copper-catalyzed azide-alkyne cycloaddition and nitroxide radical coupling click reactions, yield resulting ABC miktoarm star polymers in a one-pot mode. (c) 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 50: 729-735, 2012