Using ethanol electrocatalytic oxidation reaction (EOR) with a lower reaction potential to replace oxygen evolution reaction (OER) and integrating hydrogen evolution reaction (HER) have a promising development prospect for more energy-saving electrolytic hydrogen production. However, the main challenges of EOR are insufficient catalytic activity, high overpotential, and slow kinetics. Active sites on the electrocatalysts surface are occupied by alkali metal ion hydrate clusters by noncovalent interactions, which is considered to be one of the major causes of these challenges. To reduce the effect of the noncovalent interactions on the catalytic activity of the electrocatalyst, copper is chosen and doped in the form of a single atom in the electrocatalyst (Pt@Cu/C) to increase the electrocatalyst conductivity and make the anode contain more positive charge in this study. Then, alkali metal ion hydrate clusters are difficult to adsorb at the active site of Pt@Cu/C. The EOR electrocatalytic activity of Pt@Cu/C is up to 8184 mA mg_Pt⁻¹, which is ≈4.8 times as high as that of Pt/C. The two-electrode hydrogen production device using Pt@Cu/C as anode for coupled EOR&HER requires a smaller voltage of 0.60 V to reach 10 mA cm⁻² compared with that of Pt/C (0.76 V).