Three types of high surface area copper electrodes were prepared by thermal spraying techniques. CuAl electrodes were obtained by thermal arc spraying of two different wires (Cu and Al) followed by the alkaline dissolution of aluminum. Cu wire and Cu powder electrodes were obtained by combustion spraying of copper wires and powders, respectively. Several methods have been used to characterize the electrodes, including scanning electron microscopy, energy dispersive X-ray analysis and X-ray diffraction. The electrocatalytic activity of the electrodes was evaluated based on the steady-state polarization curves and electrochemical impedance data. It has been found that the structure of the prepared electrodes depends to a great extent on the deposition method, i.e. combustion spraying gives deposits with higher surface roughness and porosity. Decreasing the particles size leads to the increase of the porosity and surface roughness and also to the increase of the copper oxide content.