In summary, we have demonstrated a convenient yet highly efficient method for the preparation of PE-based graft copolymers via ATRP. By introducing a small amount of styrene groups into PE chains via the selective copolymerization of ethylene with 1,4-divinylbenzene catalyzed by Et(Ind)₂ZrCl₂/MAO, the multifunctional ATRP initiator of 1-chloroethylbenzene-containing PE was readily achieved by a quantitative hydrochlorination reaction and was shown to be very effective for the initiation of graft polymerization of MMA and styrene to prepare structurally well-defined PE-based graft copolymers.