Ammonia (NH3) plays a vital role in industrial and agricultural development. The electrocatalytic nitrate reduction reaction (eNO3RR) is an effective method to produce NH3under environmental conditions but also requires considerably active and selective electrocatalysts. Herein, a copper foam was used as a conductive substrate for the electrode materials. Specifically, a Co metal–organic framework (Co-MOF) was in situ grown on the copper foam, etched, and calcined to form NiCoO2@Cu nanosheets, which were used as cathode electrodes for the eNO3RR. In 0.1 M Na2SO4with 0.1 M NaNO3electrolyte, NiCoO2@Cu nanosheets realized an NH3yield of 5940.73 μg h–1cm–2at −0.9 V vs reversible hydrogen electrode (RHE), with a Faradaic efficiency of 94.2% at −0.7 V vs RHE. After 33 h of the catalytic reaction, the selectivity of NH3–N increased to 99.7%. The excellent electrocatalytic performance of NiCoO2@Cu nanosheets was attributed to the apparent synergistic effect between the Ni atoms and the Co atoms of bimetallic materials. This study shows that the Ni doping of NiCoO2@Cu nanosheets effectively facilitated the adsorption of NO3–on NiCoO2@Cu, and it promoted the eNO3RR.