Cu monolayer/electrochemically reduced graphene oxide (ML/ERGO) layered nanocomposites are grown on Au substrates by sequential underpotential deposition of Cu(ML)s and electrochemical reduction of graphene oxide for the electrocatalytic oxidation of ethanol. Characterization of the Au-Cu(ML)/ERGO layered composites by scanning electron microscopy and scanning tunneling microscopy reveal that the smooth Cu(ML) on the Au surface is transformed into parallel aligned nanoparticles after modification by the ERGO layer. X-ray photoelectron spectroscopy and Raman spectroscopy results for the Au-Cu(ML)/ERGO composites show the successful electrochemical reduction of GO to ERGO and the presence of metallic Cu in the nanocomposite structure. Electrochemical measurements of the as-prepared Au-(Cu(ML)/ERGO)(1) electrodes exhibit excellent electrocatalytic performance (15 mA cm(-2)), which was 5.7 and 1.6 times higher than those from the naked Au and Au-Cu(ML) electrodes, respectively, toward ethanol electro-oxidation in alkaline condition.