Understanding from the underlying mechanism of chain shuttling polymerization (CSP) is limited due to scarceness of successful reports and incompetence of traditional characterization techniques to distinguish blocky structures. Here, a simple synthesis approach for production of an isotactic poly(1-hexene)/branched polyethylene multiblock copolymer from a 1-hexene monomer is presented. Resulting copolymers can be easily characterized because of their solubility in most organic solvents. This novel blocky architecture is synthesized using ansa-ethylenebis(1-η5-indenyl)zirconium dichloride and α-diimine nickel(II) bromide catalysts. While the former participates in 1,2-enchainment of monomers and produces amorphous segments, the latter forms methylene sequences through chain walking reaction. A quasi-living polymerization is established by reversible transfer of growing chains between catalyst components, as manifested by narrowing molecular weight distribution. 13C NMR analysis confirms that the blocky st...