Reaction of N-phenyl-pivalohydroxamic acid with Ce^III precursors leads to a homoleptic hydroxamate complex: Ce^IV[^tBuC(O)N(O)Ph]₄. Electrochemical experiments indicate a significant stabilization of the Ce^IV cation at E_p,c = −1.20 V versus SCE in the hydroxamate ligand framework. The spontaneous oxidation of Ce^III in a hydroxamate ligand field is discussed in the context of beneficiation of the light rare earths from the fluorocarbonate mineral bastnäsite.