A simple electrochemical method is employed to synthesize nanoparticles of bimetallic PtPd alloy on Nafion–graphene film. The alloy nanoparticles exhibit efficient electrocatalytic activity and stability toward ethanol oxidation in alkaline media. With the synergetic effects of the PtPd nanoparticles and the enhanced electron transfer stem from graphene, this anode catalyst has higher current density than the monometallic Pt or Pd catalyst. Moreover, this anode catalyst has a low onset potential at −0.73 V (vs. Ag/AgCl) and a high ratio of forward peak current density to backward peak current density (I_f/I_b) of 5.45. The results indicate that the catalyst has good tolerance against poisoning by intermediates generated during ethanol electro-oxidation and is effective in cleaving the C–C bond to achieve oxidation of ethanol to CO₂.