A new vanadyl(V) complex with the tridentate, pincer-type O,S,O-ligand thiobis(phenolate), tbp, was synthesized from the reaction of vanadium(IV) oxide bis(acetylacetonate), VO(acac)2, and 2,2’- thio-bis(4-methylphenol), H2tbp, in refluxing methanol in high yield. Single-crystal X-ray diffraction structure analysis revealed for VO(tbp)(acac) that the vanadium atom is octahedrally coordinated with an O5,S-donor environment where the thiobis(phenolate) ligand is O,S,O-bonded to the vanadyl(V) center facially in a tridentate dinegative fashion. Cyclic voltammetric experiments carried out with its solution in dimethyl sulfoxide revealed an irreversible peak at −0.768 V (vs. Ag/AgCl) relating to the V5+/V4+ reduction process.