Herein, the reduction of the Cu oxidation state during the CO2 electro-reduction reaction (CO2RR) is effectively inhibited by depositing C60 supramolecular clusters onto the Cu(OH)F surface. By utilizing the unique electronic buffering capacity of C60, a significant number of Cu0/Cu+ sites are created, leading to a remarkable faradaic efficiency of C2+ products up to 76.9% and exceptional stability.