<p>The use of renewable electricity to drive the electrocatalytic coupling of CO with nitrogen-containing organics offers a promising strategy for producing high-value chemicals. In this work, we conduct a systematic investigation of the coordination effect between iodide and copper oxide to generate Cu^δ+ active sites. These Cu^δ+ sites enable the electrosynthesis of dimethylacetamide from CO and dimethylamine. Through precise regulation of the electrode surface microenvironment, a dimethylacetamide Faradaic efficiency of 45.6% is achieved at a partial current density of 182.4 mA·cm^-2, with a production rate of 435.9 mmol·g_cat.⁻¹·h^-1 and selectivity approaching 70%. Mechanistic studies reveal that specific adsorption of I^- forms an iodide-enriched Cu⁰/Cu⁺ interface that synergistically promotes dimethylacetamide formation by enhancing adsorption of ketene intermediates (*CCO) and facilitating C–N bonds formation. This anion-coordination interfacial engineering strategy demonstrates broad applicability for synthesizing various acetamide derivatives from CO₂/CO and amine, providing a foundational framework for electrocatalytic C-N coupling in acetamide synthesis.</p>