A new heterobifunctional initiator, 2,3-bis(2-bromo-2-methylpropionyloxy) succinic acid, was synthesized and used in preparation of A(2)B(2) miktoarm star copolymers, (polystyrene)(2)(poly(epsilon-caprolactone))(2), by combination of atom transfer radical polymerization (ATRP) and Controlled ring-opening polymerization (ROP). The structures of products were confirmed by the H-1 NMR, C-13 NMR, FT-IR, elemental analysis, differential scanning calorimetry (DSC), and gel permeation chromatography (GPC). GPC traces show that the obtained polymers have a relatively narrow molecular weight distribution. The compositions of resulting miktoarm star copolymers were very close to theoretical.