Copper‐based catalysts are frequently employed for carbon dioxide reduction reactions (CO2RR), yet the regulation of pore structure and surface state of electrocatalysts remains a prominent challenge in previous research endeavors. In this study, we introduce a novel technique to produce mesoporous Cu2O nanocrystals, with finely tuned pore size and surface amine functionality leveraging the incorporation of various amine compounds during the oxidative process of copper nanocrystals. The synergistic effect of pore structure confinement and surface amine functionalization culminates in an impressive Faradaic efficiency (FE) of 51.9% for the selective production of C2H4. More details are discussed in the article by Huang et al. on page 1846—1852.image