The kinetics of vanadate release from an organic coating and the stability and protective ability of the newly formed vanadate-based films on zinc surfaces have been studied with respect to self-healing ability of vanadate-pigmented organic coatings. The results were compared with those obtained with chromate. The kinetics of vanadate release from a polyester coating was comparable to that of chromate. The methods of X-ray absorption near edge spectroscopy (XANES) and scanning Kelvin probe were used for studying the mechanism of inhibition and the kinetics of vanadate reduction on bare zinc. XANES proved to be a powerful tool for determination of the oxidation state of vanadium in surface films. The experiments showed that vanadate was reduced more rapidly than chromate under the same atmospheric conditions. However, addition of magnesium phosphate resulted in a significantly lower reduction rate of vanadate. The results are discussed in light of the increased adsorption ability of the more negatively charged vanadium(V) species at higher pH, while the oxygen reduction process on zinc is inhibited due to the presence of phosphate. Thus, vanadate in combination with another inhibitor could provide corrosion protection at defects of organic coatings on zinc comparable to that of chromate.