In the paper, the glow discharge optical emission spectroscopy, X‐ray photoelectron spectroscopy, scanning electron microscopy, and energy‐dispersive X‐ray spectroscopy results of a commercial purity titanium grade 2 after plasma electrolytic oxidation (PEO), also known as micro arc oxidation (MAO), are presented. The PEO treatment was performed in the electrolyte containing concentrated (85%) phosphoric acid with copper nitrate at the voltage of 450 ± 10 V for 1 min. For the electrolyte, copper nitrate addition from 300 to 600 g/l was used. Porous coatings of specific properties were obtained. The measurements results allow to state that the copper and nitrogen ions can be introduced into the surface layer formed on pure titanium by the plasma electrolytic oxidation. The distributions of these elements were detected to depend on the electrolyte composition, with the highest amounts revealed in the coating created in the electrolyte containing 600 g Cu(NO3)2 in 1 l H3PO4. Three sub‐layers of the coating, displayed in this work by two models, were developed in the study. The analysis performed shows that under the PEO treatment in each of the electrolytes used, the formation of coating with the top sub‐layers always enriched in copper compounds was found. Copyright © 2016 John Wiley & Sons, Ltd.