Ammonia is a safe and efficient hydrogen carrier, and electrocatalytic ammonia oxidation reaction (AOR) is a pivotal anodic process for ammonia decomposition to produce hydrogen. Although previous works have devoted to reducing the reaction potential, concurrently achieving a high Faradaic efficiency (FE) for nitrogen (N2) remains a substantial challenge, particularly across a broad potential range. Here, Ni and Cu nanoparticles anchored nickel metal–organic framework (Ni-NDC) electrocatalyst is successfully synthetized. During the AOR process, the surface catalyst could be evolved into stable NiOOH. The well-dispersed Ni and Cu nanoparticles on the Ni-NDC facilitate a unique interaction between Cu and both the Ni nanoparticles and the Ni-NDC framework. With the incorporation of Cu, the adsorption of hydroxyl (*OH) is impaired to suppress the formation of oxygen-containing by-products (such as NO3– and NO2–) across a wide potential range. Consequently, the FE(N2) is markedly high (approximately 90%). Additionally, the reaction kinetic is also improved, resulting in a lower reaction potential for AOR. This work provides an effective method for synthesizing high-performance AOR electrocatalysts.