Homogeneous nickel catalysis is used for the synthesis of pharmaceuticals, natural products, and polymers. These reactions generally proceed via nickel intermediates in the Ni-O, Ni-I, Ni-II, and/or Ni-III oxidation states. In contrast, Ni-IV intermediates are rarely accessible. We report herein the design, synthesis, and characterization of a series of organometallic Ni-IV complexes, accessed by the reaction of Ni-II precursors with the widely used oxidant S-(trifluoromethyl) dibenzothiophenium triflate. These Ni-IV complexes undergo highly selective carbon(sp(3))-oxygen, carbon(sp(3))-nitrogen, and carbon(sp(3))-sulfur coupling reactions with exogenous nucleophiles. The observed reactivity has the potential for direct applications in the development of nickel-catalyzed carbon-hetero-atom coupling reactions.