The blocked copolymers of polydivinylbenzene block hyperbranched polyethylene were successfully synthesized via in situ copolymerization by Atom Transfer Radical Polymerization (ATRP) method, in which hyperbranched polyethylene capping reactive functional terminal groups were used as macro-comonomers. Hyperbranched polyethylene branches capping functional terminal groups are obtained by injecting divinylbenzene in ethylene “living” polymerization system via end–quenching reaction. The various macro-comonomers have terminal reactive groups on hyperbranched polyethylene branches obtained by varying temperature, pressure, co-monomer type or structure and feed processing duration in chain walking ethylene “living” polymerization processes. It may provide a new way for directly preparing polyolefin-based functionalized block copolymers by various polyolefin-based macro-comonomers. The resulting polydivinylbenzene block hyperbranched polyethylene copolymers have still relatively narrow distribution of molecular weights (around 1.18), predetermined molecular weights, and good compatibilities with polar and nopolar polymers.