The microspark oxidation (MSO) (also known as microarc oxidation (MAO) or plasma electrolytic oxidation (PEO)) is one of the methods used for the formation of oxide coatings on valve metals. The main advantage of the MSO method, along with many others, consists in the simplicity of the technology of formation of films having a high adhesion to a metal substrate. The method enables one to obtain high-quality porous anode oxide films for different applications: antifriction, anticorrosion, for sensor materials, etc. In this work, the anode oxide films consisting of a mixture of three modifications of zirconia and a silica amorphous phase were formed on a zirconium foil from a sodium silicate aqueous solution by means of the MSO method.