In this work the effect of thermal annealing on the surface composition, structure and catalytic activity in CO oxidation of NiO + CuO/TiO2/Ti composites is studied. The composites have been obtained by a plasma electrolytic oxidation (PEO) technique, followed by impregnation in a solution of nickel (II) and copper (II) salts and air annealing. The structures contain similar to 20 at% Ni and similar to 12 at% Cu. It has been shown that the additional air annealing of such structures at temperature above 750 degrees C results in phosphate crystallization in the coatings and decreasing of Cu concentration in the surface layers. A growth of filiform nanocrystals containing mainly oxygen compounds of nickel and titanium on the coating surface takes place at the temperatures above 700 degrees C. The nanocrystals have a diameter of 50-200 nm and lengths below 10 mu m. Such changes result in decreasing of catalytic activity of the composites in CO oxidation. At the same time the ascertained regularities may be of interest for obtaining the Ni-containing oxide catalysts with an extended surface, perspective for usage in organic catalysis or for preparing oxide nanofibers. (C) 2012 Elsevier B.V. All rights reserved.