Cuprous oxide (Cu2O) materials are the most promising copper-based catalysts for electrochemical nitrate (NO3–) reduction to ammonia (NH3). Nevertheless, adsorption for N–containing intermediates (NO3–, NO2–, etc.) is too–strong, and combined with their limited hydrogenation capacity, reduces their capacity for efficient NH3 synthesis via alkaline electrochemical NO3– reduction reactions (eNO3–RR). Herein, we present a Cu2O catalytic electrode incorporating iron with a pyramid–like structure, fabricated on a copper foam (CF) matrix, obtained through an “electroplating–oxidation–electroreduction” (E–O–E) strategy. The incorporation of Fe regulates the local charge modulation environment and micromorphology of the Cu2O, creating Fe3+ and Cu+ dual active sites in the Cu2O/CF that accelerate the rate of hydrogenation. Calculations reveal that the incorporated Fe3+ shift the d–band center of Cu2O to the Fermi level and decrease the adsorptive free energies of bound N containing intermediates, facilitating the eNO3–RR reaction. The optimal Fe–Cu2O catalyst exhibits excellent performance in the eNO3–RR, achieving an NH3 yield rate of 10.27 mg h–1 cm–2 and a FE reaching 93.05 %. The catalytic performance remains stable at –0.3 V vs. RHE for 20 h under alkaline conditions, implying its outstanding durability. Consequently, this work highlights the potential of dual active sites via heteroatomic incorporation to boost the eNO3–RR process and provides new insights for developing advanced electrocatalysts.