The rough Cu film was prepared by electrochemical reduction of copper ions at the surface of gold film electrode (GFE). Nanostructured Cu/Pt catalyst was prepared by partially galvanic replacement of Cu with platinum by simply immersion of Cu-coated gold film electrode in a K2PtCl6 aqueous solution. The structure and nature of the fabricated Cu and Cu/Pt species were characterized by scanning electron microscopy and energy dispersive X-ray spectrometry. Cu-/Pt-coated gold film electrode exhibits really high electrochemical active surface area and remarkable electrocatalytic activity toward methanol oxidation. The effect of electrodeposition potential on the stability of the catalyst during the formation of Cu layer was comparatively investigated by performing methanol oxidation using voltammetry methods.