In summary, Cu-based bimetallic catalysts exhibit outstanding activity and selectivity in CO₂RR, attributed to the distinctive electronic structure and adsorption energy of key intermediates. Furthermore, the leaching and re-deposition mechanism of the amphoteric metal (Zn, Al), influenced by the strong alkaline electrolyte and reduction potentials, has been demonstrated to play a crucial role in the performance of Cu-based bimetallic catalysts. In conclusion, this study not only introduces an effective strategy for designing efficient Cu-based catalysts for CO₂RR towards C₂₊ products but also provides new insights into the surface reconstruction of amphoteric metal-doped Cu₂O catalysts.