The methods of X-ray photoelectron spectroscopy and Auger spectroscopy are used to study surface films formed on zinc and zinc-plated steel in the process of holding in aqueous extracts of mixtures of phosphate and calcium-containing pigments. It is shown that protective films formed mainly of zinc and calcium phosphates of different chemical structure are deposited in inhibited solutions on specimens of pure zinc and zinc-plated steel. The protective properties of these films are much better than the protective properties of the surface layers formed on the metal in the extracts of a single phosphate (or calcium-containing) pigment. The mixture of these pigments may serve as a promising substitution of chromate inhibitors in anticorrosive organic coatings.