Styrene/N-cyclohexylmaleimide copolymers with small polydispersities and controlled molecular weights were synthesized by a free radical copolymerization using an iniferter system consisting of benzoyl peroxide and 2,2,6,6-tetramethylpiperidine-N-oxyl. Due to the interactions of the electropositive (styrene) and electronegative (N-cyclohexylmaleimide) monomers the brutto polymerization rates are higher than for other living polymerizations initiated with the same iniferter system. The prepared copolymers were used as macroiniferters for bulk polymerization of styrene.