A novel linear-hyperbranched multiblock polyethylene was prepared from ethylene monomer alone via chain walking and chain shuttling polymerization in the presence of chain transfer agent (ZnEt2). In the binary catalyst system, alpha-diimine nickel(II) bromide complex (CatA) produced chain segments with hyperbranched architecture via chain walking, and ansa-ethylenebis(1-eta(5)-indenyl)zirconium dichloride (CatB) yielded linear chain segments, while ZnEt2 facilitated chain exchanges between two active metal centers. The resultant multiblock polyethylene featured a narrow weight distribution and useful combining properties of linear and branched polyethylene. Further, polymers were expediently prepared in an effective and economical polymerization process from ethylene monomer alone.