Oxidovanadium complexes have previously been used for the oxidation and kinetic resolution of sulfides and sulfoxides, respectively. In 2005, Toste and co-workers demonstrated an efficient kinetic resolution of α-hydroxy acid derivatives catalyzed by an oxidovanadium complex (A. T. Radosevich, C. Musich, F. D. Toste J. Am. Chem. Soc. 2005, 127, 1090). The authors report a study of the vanadium-catalyzed kinetic resolution of α-hydroxy ketones. During this study several ligands are examined and various substituted benzoin adducts are investigated under optimized conditions, expanding the scope of vanadium-catalyzed kinetic resolutions.