The synthesis and characterization of a series of nickel complexes bearing a bismuth-containing pincer ligand are presented herein. In particular, synthesis of a 4-coordinate Bi-Ni(II) complex allows the influence of bismuth on a d8 Ni(II) ion to be investigated. A trigonal-bipyramidal complex, (BiP2)Ni(PPh) (1), possessing an anionic bismuth donor was prepared via the Bi-C bond cleavage of a BiP3 ligand (BiP3 = Bi(o-PiPr2-C6H4)3) mediated by Ni(0). To remove a PPh moiety, compound 1 was treated with MeI to give a 5-coordinate nickel(II) complex (MeBiP2)Ni(PPh)(I) (2), followed by its exposure to heat or UV irradiation, resulting in the formation of a nickel halide complex, (BiP2)Ni(I) (3). The X-ray crystal structure of 2 revealed that the methyl moiety binds to a bismuth site, providing a neutral MeBiP2 ligand, while the iodide anion is bound to the nickel(II) center, displacing one phosphine donor. Because of the methylation on a Bi site, the Bi-Ni bond in 2 is clearly elongated relative to that of 1, which indicates that the bonding interactions between Bi and Ni are substantially different. Interestingly, compound 3 revealing a sawhorse geometry is significantly distorted away from a square-planar structure compared to the previously reported nickel(II) pincer complexes, (NP2)Ni(Cl) and (PP2)Ni(I). Such difference indicates that a bismuth donor can be a structurally influencing cooperative site for a nickel(II) ion, leading to have a Ni(I)-Bi(II) character. Migratory insertion of CO into a Ni-C bond of 1 gives (BiP2)Ni(COPPh) (4), which further leads to an analogous methylated product (MeBiP2)Ni(COPPh)(I) (5) from reaction with MeI. Due to the structural influence of a carbonyl group in each step, the total reaction time from 1 to 3 was dramatically reduced. The bimetallic cooperativity of the complexes and unusual bonding properties presented here highlight the potential of a bismuth-nickel moiety as a new type of heterobimetallic site for the design of bimetallic complexes to facilitate a variety of chemical transformations.