Reaction of the oxidovanadium(IV)-LN-N species (LN-N is bipy = 2,2'-bipyridine or bipy-like molecules) with either BF4- or HF and/or KF results in the formation of compounds of the general formula cis-[V-IV(=O)(F)(LN-N)(2)](+). Structural and spectroscopic (electron paramagnetic resonance) characterization shows that these compounds are in the tetravalent oxidation state containing a terminal fluorido ligand. Density functional theory calculations reveal that the V-IV-F F bond is mainly electrostatic, which is reinforced by reactivity studies that demonstrate the nucleophilicity of the fluoride ligand in a halogen exchange reaction and in fluorination of various organic substrates.