Polyarylether dendrons as macroinitiators for the “living”/controlled free radical copoly-merization of N-phenylmaleimide (PhMI) and styrene (St) have been demonstrated. The copoly-merization was carried out in bulk or anisole with CuBr/bipy catalyst at 100-130℃. It is found that the resulting copolymers possess predetermined molecular weights and narrower polydispersities (1.18 < Mw/Mn<1.32). The effects of reaction temperature and monomer feed on the copolymeri-zation kinetics were investigated in detail. By using the Fineman-Ross method, the apparent monomer reactivity ratios for the atom transfer radical copolymerization of PhMI and St were determined to be rphM1 = 0.0207, and rst = 0.0484, respectively. Polyarylether dendrons as macroinitiators for the “living” / controlled free radical copoly-merization of N-phenylmaleimide (PhMI) and styrene (St) have been demonstrated. The copoly- merization was carried out in bulk or anisole with CuBr / bipy catalyst at 100-130 ° C. The effects of reaction temperature and monomer feed on the copolymeri-zation kinetics were investigated in detail. By using the Fineman-Ross method, the apparent monomer reactivity ratios for the atom transfer radical copolymerization of PhMI and St were determined to be rphM1 = 0.0207, and rst = 0.0484, respectively.