Two kinds of ABC-type miktoarm star copolymers, poly(α-methylstyrene)-poly(ethylene oxide)-poly(ethoxyethyl glycidylether) (PMS-PEO-PEEGE) and poly(α-methylstyrene)-poly(ethylene oxide)-polyglycidol (PMS-PEO-PG), were synthesized via a combination of anionic polymerization with ring-opening polymerization. Firstly, The poly(α-methyl styryl lithium) (PMS－Li+) was capped by EEGE to form the functionalized poly(α-methylstyrene) with both an active ω-hydroxyl group and an ω’-ethoxyethyl-protected hydroxyl group. Secondly, the PMS-b-PEO block copolymers, star(PMS-PEO-PEEGE) and star(PMS-PEO-PG) copolymers were obtained by the ring-opening polymerization of EO and EEGE via the variation of the functional end group, respectively. Finally, the ethoxyethyl group on the PEEGE arm was hydrolyzed. The obtained miktoarm star copolymers and intermediates were characterized by proton nuclear magnetic resonance (1H-NMR) and size exclusion chromatography (SEC).