Peculiarities of plasma-electrolytic oxidation of the aluminum alloys in diphosphate electrolytes are discussed. It is shown that PEO parameters depend on the composition and concentration of the components of the working solutions. The mechanism of cobalt oxides incorporation into the composition of surface layers is proposed. It has been established that the oxidation of titanium in citrate-diphosphate electrolytes promotes the formation of mixed oxide layers TiOx·CoOy. The obtained mixed oxide systems have a developed microporous globular-toroidal surface and are characterized by a complex of enhanced functional properties - corrosion and abrasion resistance, catalytic activity in the carbon (II) oxide conversion reaction.