A nickel alpha-keto-beta-diimine initiator (1), when activated with methylaluminoxane (MAO) generates active sites capable of polymerizing alpha-olefins to high molecular weight products. Herein, we report on the full characterization and detailed microstructural analysis of poly(1-hexene) (PH) homopolymers obtained by using the 1/MAO combination. C-13 NMR spectroscopy was used to provide the First qualitative and quantitative determinations of all the sequences in the poly(1-hexene). Such information yields insight into the reactivity of this novel catalytic system.