Symmetric and asymmetric Ni(II) diimine complexes such as 2-[(2,6-diisopropylphenylimino)methyl]pyridine nickel(II) dibromide (a), 2-[1-(2,6-diisopropylphenylimino)ethyl]pyridine nickel(II) dibromide (b) and [1,2-bis(2,6- diisopropylphenylimino)]acenaphthene nickel(II) dibromide (c) were synthesized. For olefin homopolymerization, asymmetric Ni(II) diimine complexes [(a) & (b)] were compared with symmetric system (c). Asymmetric Ni(II) diimine complexes exhibited less catalytic activity and thermal stability as well as more b-hydride elimination than a symmetric diimine complex (c). The activity of (a) was larger than that of (b), which indicates that methyl group has a contribution to the instability of catalyst by s bond vibration rather than the stabilization of the active site by electron releasing property.