Novel calixarene centered amphiphilic A(2)B(2) mik toarm star copolymers composed of two PCL arms and two PEG arms with calix[4]arene as core moiety were synthesized by the combination of CROP and click chemistry First a heter otetrafunctional calix[4]arene derivative with two hydroxyl groups and two alkyne groups was designed as a macroinitiator to prepare calixarene centered PCL homopolymers (C4 PCL) by CROP in the presence of Sn(Oct)(2) as catalyst at 110 degrees C Next azide terminated PEG (A PEG) was synthesized by tandem treating methoxy poly(ethylene glycol)s (mPEG) with 4 chlorobutyryl chloride and NaN3 Finally copper(I) catalyzed cycloaddition reaction between C4 PCL and A PEG led to A(2)B(2) miktoarm star copolymer [C4S(PCL)(2) (PEG)(2)] H-1 NMR F IR and SEC analyses confirmed the well defined miktoarm star architecture These amphiphilic miktoarm star copolymers could self assemble into multimorphological aggregates in water The calix[4]arene moieties with a cavity <1 nm on the hydrophilic/hydrophobic inter face of these aggregates may provide potential opportunities to entrap guest molecules for special applications in supermolecular science (c) 2010 Wiley Periodicals Inc J Polym Sci Part A Polym Chem 48 5643-5651 2010