In the paper, the scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), and Xray photoelectron spectroscopy (XPS) results of the Ti6Al4V alloy treated by a novel plasma electrolytic oxidation (PEO) (micro arc oxidation) in the electrolyte containing concentrated phosphoric acid and copper nitrate are presented. The PEO treatment was performed at the voltage of 450±10 V. The main problem to solve under the experiments was to obtain a porous surface layer composed mainly of titanium phosphates within the copper ions. The performed study has shown that the amount of copper nitrate in 85 % concentrated phosphoric acid should be not less than 1