A novel-Pd/CuO–Ni(OH)₂/C catalyst utilizing carbon black as a support was successfully synthesized using hydrazine hydrate reduction and galvanic replacement strategies and was subsequently tested for activity in the electrocatalytic oxidation of ethanol. The observed peak current density (3.74 A mg_Pd⁻¹) for Pd/CuO–Ni(OH)₂/C was 19.68 times higher than that of commercial Pd/C (0.19 A mg_Pd⁻¹). The as-synthesized Pd/CuO–Ni(OH)₂/C (hereafter denoted as PdCuNi/C) catalyst exhibited a significantly improved electrocatalytic activity and durability compared with Pd/C, PdNi/C, PdCu/C and the PdCuNi/C catalysts reduced in N₂/H₂ at different temperatures. The reason for this is that the high dispersion of Pd resulted in the exposure of more active sites on the surface of the catalyst. The excellent CO₂ selectivity of Pd/CuO–Ni(OH)₂/C (22.5%) for the ethanol electronic oxidation reaction (EOR) was observed using in situ Fourier transform infrared spectroscopy (FTIR) spectra and could be attributed to the synergistic effect of Pd, CuO and Ni(OH)₂ and the presence of the OH_ad adsorption at Ni(OH)₂ at a low potential.