Cyclic voltammograms for stationary and rotating vanadium disc electrodes were obtained in aqueous solutions over a wide pH range. A number of multiple-cycle potential programs were employed. The repetitive cycling was accompanied by a gradual accumulation of an adsorbed layer at the vanadium electrode surface. The chemical nature of the layer was independent of pH, and was assigned as V(III) oxyhydroxide intermediates in the process of anodic dissolution of vanadium. The two major voltammetric features were the oxidation of V(III) oxyhydroxide to V(IV), and the reduction of V(IV) oxide species to V(III). Different rate-determining steps were shown to govern the anodic dissolution of vanadium in acidic and alkaline solutions.