The direct ethanol fuel cell is a green and renewable power source alternative to fossil fuels and produces less emissions compared to a combustion engine. Ethanol can be generated in great quantity from renewable resources like biomass through a fermentation process. Bio-generated ethanol is thus attractive fuel since growing crops for biofuels absorbs much of the carbon dioxide emitted into the atmosphere from the oxidation of ethanol. The platinum and palladium were co-deposited on graphite substrate by the galvanostatic technique and employed as anode catalyst for ethanol electrooxidation. The information on surface morphology, structural characteristics and bulk composition of the catalyst was obtained using scanning electron microscopy (SEM), X-ray diffraction (XRD) and energy dispersive X-ray (EDX) spectroscopy. The cyclic voltammetry (CV) were used for the estimation of the electrochemically active surface area (ECSA) of the synthesized catalysts in alkaline medium. The CVs for ethanol oxidation revealed superior catalytic activity of Pt–Pd/C compared to Pd/C and Pt/C. The effect of OH− on ethanol oxidation at Pt–Pd/C catalyst was studied using cyclic voltammetry, quasisteady-state polarization, chronoamperometry, and electrochemical impedance spectroscopy (EIS). The Pt–Pd/C catalyst shows good stability and enhanced electrocatalytic activity is ascribed to the synergistic effect of higher electrochemical surface area, preferred OH− adsorption on the surface and palladium ad-atom contribution on the alloyed surface.