Star copolymers of M-n varying between 20 000 and 80 000, containing a hydrophobic branched poly[p-(chloromethyl)-styrene] core and hydrophilic polyether shell, were synthesized. The core was obtained via atom transfer radical polymerization of p-(chloromethyl)styrene. Some of the chlorine groups in the core were reacted with living polyether macroanions, yielding amphiphilic star structures in the Williamson etherification reaction.