DFT calculations were used to investigate the detailed mechanism, chemoselectivity of the ligand-controlled chemoselectivity-switchable Ni-catalyzed C−N cross-coupling of amine. The post-intermediate of the anion exchange is the resting state of the overall catalytic cycle, and the C−N reductive elimination of the Ni(II) complex is the turnover-limiting step. The intrinsic electronic effect of the substrates and ligand-control the chemoselectivity, leading to the preference of the C−N cross coupling.