Controlled electrosynthesis of poly(N-ethylaniline) (PNEA) layer is demonstrated on copper nanowires supported by a copper foil. Copper nanowires were grown by thermal oxidation/reduction of copper foil support. Potentiodynamic electropolymerization provides control over morphology resulting in the formation of polymer layer on copper nanowire electrode showing stable adhesion and homogeneous deposition. The resulting polymer coating can support electrochemically active metal nanoparticles (NPs) that can be introduced in a separate step. Here, we chose copper nanoparticles as electrocatalyst. The Cu NP/PNEA/Cu nanowire electrode was characterized for glucose and methanol electrochemical oxidation to demonstrate the versatility of the polymer-coated copper nanowire structure for electrochemical reactions in aqueous solution.