A new air-stable catalyst for the oxidative dehydrogenation of benzylic alcohols under ambient conditions has been developed. The synthesis and characterization of this compound and the related monomeric and dimeric V­(IV)- and V­(V)-pinF (pinF = perfluoropinacolate) complexes are reported herein. Monomeric V­(IV) complex (Me4N)2[V­(O)­(pinF)2] (1) and dimeric (μ-O)2-bridged V­(V) complex (Me4N)2[V2(O)2(μ-O)2(pinF)2] (3a) are prepared in water under ambient conditions. Monomeric V­(V) complex (Me4N)­[V­(O)­(pinF)2] (2) may be generated via chemical oxidation of 1 under an inert atmosphere, but dimerizes to 3a upon exposure to air. Complexes 1 and 2 display a perfectly reversible VIV/V couple at 20 mV (vs Ag/AgNO3), whereas a quasi-reversible VIV/V couple at −865 mV is found for 3a. Stoichiometric reactions of 3a with both fluorenol and TEMPOH result in the formation of (Me4N)2[V2(O)2(μ-OH)2(pinF)2] (4a), which contains two V­(IV) centers that display antiferromagnetic coupling. In order to structurally characterize the dinuclear anion of 4a, {K­(18C6)}+ countercations were employed, which formed stabilizing K···O interactions between the counterion and each terminal oxo moiety and H-bonding between the oxygen atoms of the crown ether and μ-OH bridges of the dimer, resulting in {K­(18C6)}2[V2(O)2(μ-OH)2(pinF)2] (4b). The formal storage of H2 in 4a is reversible and proton-coupled electron transfer (PCET) from crystals of 4a regenerates 3a upon exposure to air over the course of several days. Furthermore, the reaction of 3a (2%) under ambient conditions with excess fluorenol, cinnamyl alcohol, or benzyl alcohol resulted in the selective formation of fluorenone (82% conversion), cinnamaldehyde (40%), or benzaldehyde (7%), respectively, reproducing oxidative alcohol dehydrogenation (OAD) chemistry known for VO x surfaces and demonstrating, in air, the thermodynamically challenging selective oxidation of alcohols to aldehydes/ketones.