Synthetic tetragonal and monoclinic vanadium-doped zirconias (t- and m-VxZr1-xO2, 0.005 < x < 0.150) exert an effective catalytic effect toward the electrochemical oxidation of glucose in aqueous alkaline media. The catalytic effect of monoclinic specimens attached to carbon and fluorine-doped tin oxide electrodes exhibits a remarkable enantioselectivity, so that catalytic currents for the oxidation of L-glucose at +0.92 V vs AgCl/Ag are considerably larger than those obtained for the oxidation of D-glucose. This enantioselectivity can be associated with the existence of a noncentrosymmetric coordination of vanadium centers in the monoclinic crystalline form of zirconia. From the electrochemical results, it can be suggested that the electrocatalytic mechanism includes the formation of glucose-vanadium surface adducts and electron transfer between catalytic centers and the substrate. The interference from chloride ions in the electrocatalytic process is significantly decreased by covering the zirconia particles with a layer of amorphous silica. These results propose that incorporation of catalytically active centers into nonsentrosymmetric sites of inorganic crystalline materials can be taken as a plausible strategy for chiral recognition via electrocatalysis.