Cathodic plasma electrolysis is a novel technique to form nanostructured layers on metallic surfaces by application of high voltage in a suitable aqueous electrolyte. In the present study, copper is treated by plasma electrolysis in 50 vol% ethanol electrolyte and coatings comprising carbon nanostructure and copper oxide are formed on the copper. The effect of some process parameters such as electrical conductivity, volume and temperature of electrolyte and ratio of anode to cathode surface area on current-voltage behaviour and subsequently coating compositions are investigated at 150 V deposition voltage. The composition and morphology of these coatings are characterized by X-ray diffraction, Raman spectroscopy and scanning electron microscopy. Different current-voltage behaviours, temperatures of substrate and the contents and energies of radicals and ions around the substrate by changes in the mentioned parameters cause different compositions from 100 vol% copper oxide to different ratios of copper oxide to carbon, the structure changing from amorphous to graphitic structure in carbon and amorphous to cubic morphology in copper oxide on the substrate. Therefore, the understanding of cathodic plasma electrolysis can be developed.