Miktoarm core-crosslinked star (CCS) copolymers featuring hydrophobic inner compartment based on poly(epsilon-caprolactone) (PCL), and hydrophilic multivalent exterior consisting of L-lysine dendritic wedges and estradiol or ferrocene moieties have been synthesized. Ring-opening polymerization (ROP) of epsilon-caprolactone (epsilon-CL) initiated by functional alcohols provides alkyne or azide end-capped linear PCL chains. Further derivatization of the hydroxyl chain ends of these hetero-telechelic macromolecules by methacrylic acid (MA), and subsequent Cu(I) mediated "click" coupling of terminal alkyne and azide groups with azide-functionalized dendritic wedge, 17 alpha-ethynylestradiol and ethynylferrocene afford well-defined linear-dendritic and linear macromonomers (MMs), respectively. Atom transfer radical polymerization (ATRP) of the MMs together with a difunctional monomer 1,4-butanediol dimethacrylate (BDMA) results in miktoarm CCS copolymers. Elucidation of the structure and composition of the intermediate and final products demonstrates effectiveness, versatility, and high degree of control displayed by the proposed synthetic sequence.