The two representative bulk polymers, polyolefin (PO) and polystyrene (PS) were molecularly connected to form PO-block-PS by sequential performance of the coordination and the anionic polymerizations in one pot. Ethylene/1-octene copolymerization was performed using a typical ansa-metallocene catalyst rac-[Me2Si(2-methylindenyl)]2ZrCl2 activated MMAO in the presence of di(alkyll)zinc to grow PO-chains attaching to zinc site. The anionic polymerization was subsequently performed by feeding nBuLi•(tmeda) (tmeda, N,N,N',N'-tetramethylethylenediamine) initiator and styrene monomer to grow PS-chains at the zinc site consequently attaching to PO-chains. Addition of tmeda played a key role in the growth of the PS-chains at the zinc site. Preparation of other type of PO-based block copolymers is an hot issue in the field of the controlled polymerization. So we found new zinc compound for Polyolefin-Polystyrene copolymers which has 4-(isopropenyl)benzyl. And researching on reactivity of a-methylstyrene.