Oxidation of Ce[N(SiMe3)(2)](3) in the presence of PF6- or BF4- afforded isolation of CeF[N(SiMe3)(2)](3). Structural and electrochemical characterization shows that this compound is in its tetravalent oxidation state and contains a terminal fluoride ligand. Spectroscopy and density functional theory have been used to characterize the Ce-F bond as ionic, which is reinforced by an initial reactivity study that demonstrates the nucleophilicity of the fluoride ligand.