Nickel anions [(MeCN)Ni(CF3)(3)](-) and [Ni(CF3)(4)](2-) were prepared by the formal addition of 3 and 4 equiv, respectively, of AgCF3 to [(dme)NiBr2] in the presence of the [PPh4](+) counterion. Detailed insights into the electronic properties of these new compounds were obtained through the use of density functional theory (DFT) calculations, spectroscopy-oriented configuration interaction (SORCI) calculations, X-ray absorption spectroscopy, and cyclic voltammetry. The data collectively show that trifluoromethyl complexes of nickel, even in the most common oxidation state of nickel(II), are highly covalent systems whereby a hole is distributed on the trifluoromethyl ligands, surprisingly rendering the metal to a physically more reduced state. In the cases of [(MeCN)Ni(CF3)(3)](-) and [Ni(CF3)(4)](2-), these complexes are better physically described as d(9) metal complexes. [(MeCN)Ni(CF3)(3)](-) is electrophilic and reacts with other nucleophiles such as phenoxide to yield the unsupported [(PhO)Ni(CF3)(3)](2-) salt, revealing the broader potential of [(MeCN)Ni(CF3)(3)](-) in the development of "ligandless" trifluoromethylations at nickel. Proof-inprinciple experiments show that the reaction of [(MeCN)Ni(CF3)(3)](-) with an aryl iodonium salt yields trifluoromethylated arene, presumably via a high-valent, unsupported, and formal organonickel(IV) intermediate. Evidence of the feasibility of such intermediates is provided with the structurally characterized [PPh4](2)[Ni(CF3)(4)(SO4)], which was derived through the two-electron oxidation of [Ni(CF3)(4)](2-).