For the first time, reduced graphene oxide (RGO) and nitrogen doped RGO (N-RGO) are prepared by the electrochemical procedure and then decorates with palladium nanoparticles via a solvothermal method to obtain Pd/RGO and Pd/NRGO. The as-synthesized electrocatalysts are characterized by transition electron microscopy (TEM), x-ray photoelectron (XPS), energy dispersive spectroscopy (EDS) and Fouriertransform infrared spectroscopy (FTIR) techniques. The bare RGO and NRGO electrodes are very active for the oxygen reduction reaction (ORR) and ethanol tolerance, providing the best performance in terms of tafel slope and onset potential. But, the resulting Pd/NRGO electrocatalyst shows outstanding electrocatalytic performance toward both ORR and ethanol oxidation reaction (EOR), including higher peak current density and low tafel slope than that of Pd/RGO, which can be related to high electrochemical active surface area of Pd/NRGO (53 m2 g1) than that of Pd/RGO (41 m2 g1). Finally, the fabricated anionic alkaline Membrane-electrode assemblies (MEAs) by using RGO, NRGO, Pd/RGO and Pd/NRGO are studied in single air-breathing direct ethanol fuel cell, as anode and cathode, with solutions of 4 M ethanol and 2 M KOH at room temperature.