Herein, we demonstrate the synthesis of a well-defined diblock copolymer consisting of isotactic polystyrene(iPS) and linear polyethylene, isotactic polystyrene-block-polyethylene(iPS-b-PE),by the combination ofsequential monomer addition and hydrogenation. Isospecific living polymerization of styrene and living trans-1,4-polymerization of 1,3-butadienewere catalyzed by 1,4-dithiabutandiyl-2,2′-bis(6-cumenyl-4-methylphenoxy) titanium dichloride(complex 1) activated by triisobutyl aluminum modified methylaluminoxane(MMAO) at room temperature to provide highly isotactic polystyrene(iPS) and 1,4-trans-polybutadiene(1,4-trans-PBD) with narrow molecular weight distribution. Furthermore, the iPS-b-1,4-trans-PBD was synthesized via sequential monomer addition in the presence ofcomplex 1 and MMAO.The hydrogenation of the 1,4-trans-PBD block was promoted by RuCl_2(PPh_3)_3 used as a catalyst to produce iPS-b-PE. Herein, we demonstrate the synthesis of a well-defined diblock copolymer consisting of isotactic polystyrene (iPS) and linear polyethylene, isotactic polystyrene-block-polyethylene (iPS-b- PE), by the combination of sequence modular addition and hydrogenation. Isospecific living polymerization of styrene and living trans-1,4-polymerization of 1,3-butadienewere catalyzed by 1,4-dithiabutandiyl-2,2’-bis (dichloromethanesulfonate) modified methylaluminoxane (MMAO) at room temperature to provide highly isotactic polystyrene (iPS) and 1,4-trans-polybutadiene trans-PBD was synthesized via sequential monomer addition in the presence of complex 1 and MMAO.The hydrogenation of the 1,4-trans-PBD block was promoted by RuCl_2 (PPh_3) _3 used as a catalyst to produce iPS-b-PE.