Well-defined amphiphilic A8B4 miktoarm star copolymers with eight poly(ethylene glycol) chains and four poly(epsilon-caprolactone) arms (R-8PEG-4PCL) were prepared using click reaction strategy and controlled ring-opening polymerization (CROP). First, multi-functional precursor (R-8N3-4OH) with eight azides and four hydroxyls was synthesized based on the derivatization of resorcinarene. Then eight-PEG-arm star polymer (R-8PEG-4OH) was prepared through click reaction of R-8N3-4OH with pre-synthesized alkyne-terminated monomethyl PEG (mPEG-A) in the presence of CuBr/N,N,N,N,N- pentamethyldiethylenetriamine (PMDETA) in DMF. Finally, R-8PEG-4OH was used as tetrafunctional macroinitiator to prepare resorcinarene-centered A8B4 miktoarm star copolymers via CROP of epsilon-caprolactone utilizing Sn(Oct)2 as catalyst at 100 degrees C. These miktoarm star copolymers could self-assemble into spherical micelles in aqueous solution with resorcinarene moieties on the hydrophobic/hydrophilic interface, and the particle sizes could be controlled by the ratio of PCL to PEG. (c) 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 2824-2833.