The combustion of fossil fuels has led to a surge in global CO2 emissions, causing environmental pollution and climate change issues that cannot be ignored. Ammonia, a green and carbon-free hydrogen energy, is emerging as a promising contender for new renewable fuels. Electrocatalytic nitrate-to-ammonia reduction reaction (NARR) is an emerging green synthesis method compared to the Haber-Bosch approach, and its performance is mainly controlled by selective hydrogenation. In this work, we report an efficient Fe@MOF-808-H2PO4−/HPO42− electrocatalyst (donated as Fe@MOF-808-P) for the electrocatalytic reduction of nitrate-to-ammonia. The results showed that the highest Faraday efficiency of NH3 (FENH3) is 90.8 ± 0.5 % at −0.9 V versus reversible hydrogen electrode (vs. RHE) in a 0.5 M potassium sulfate (K2SO4) solution containing nitrite (NO3−), the corresponding NH3 yield and specific activity are 420.4 ± 18.1 μmol h−1 cm−2 and 1035.9 ± 20.1 mgNH3 h−1 mgFe, respectively.Furthermore, a comparative analysis of the catalytic performance of Fe@MOF-808-H2O, MOF-808, MOF-808-P, and carbon cloth (CC) revealed that introducing P could accelerate the hydrogenation process of NO3− in the NARR process, confirming that Fe is the primary active center. Additionally, the cyclic electrolysis experiment demonstrated that the catalyst showed excellent stability. The results highlighted the promising potential of ammonia for future applications in renewable energy systems.