<p>The electrocatalytic synthesis of amides from abundant small molecules offers a sustainable route for green chemical production, yet faces fundamental challenges due to kinetic competition between C–C and C–N bond formation. Here we show an atomically engineered dual-site catalyst featuring nickel single atoms adjacent to copper nanoclusters (Ni-SA/Cu-NCs) on a nitrogen-doped carbon matrix for efficient CO₂ and NO₃⁻ co-reduction to acetamide. This architecture enables complementary functions, with Ni sites selectively converting CO₂ to CO and neighboring Cu nanoclusters promoting C–C coupling to form the *CCO intermediate while concurrently reducing NO₃⁻ to form the *NH₂ intermediate. The resulting synergy facilitates rapid intermediate transfer and C–N coupling, delivering an acetamide yield rate of 257.3 mmol h⁻¹ g_cat.⁻¹ at an industrial current density of 215.7 mA cm⁻², with stable operation over 160 h. In situ spectroscopic studies and theoretical calculations suggest that strong Ni–Cu electronic coupling promotes reactant adsorption and reduces the activation barriers for critical steps, including *CO dimerization and *CCO–*NH₂ coupling. This work provides an atomic-level design strategy for multi-site catalysts to steer complex electrocatalytic reactions toward value-added products.</p>