Bioinspired Mo‐on‐Cu Nanosheets Enable Potential‐Dependent Electrosynthesis of Urea and Methanol via Interfacial Electron Redistribution

ABSTRACT The electrochemical reduction of CO 2 and its co‐reduction with NO 3 − ions provide green pathways for the sustainable synthesis of methanol and urea; however, achieving the selective production of both compounds at low potentials remains a challenge. Inspired by natural Mo‐containing enzymes, we develop Mo‐on‐Cu nanosheets (Mo‐Cu NSs) via electrochemical reduction of CuO NSs followed by Mo deposition through electron‐beam evaporation. The bioinspired Mo‐Cu NSs deliver outstanding activity, achieving a urea partial current density of 2.39 mA cm −2 with a Faradaic efficiency (FE) of 52% at −0.2 V versus RHE, and a methanol FE of 65% at −0.5 V versus RHE, ranking among the most efficient electrocatalysts for co‐synthesis of urea and methanol. In situ electrochemical characterizations and density functional theory (DFT) calculations reveal that interfacial electron redistribution between electron‐rich Cu and electron‐deficient Mo optimizes intermediate conversion pathways, thereby enabling potential‐dependent product selectivity. Specifically, *CO 2 and *NOH coupling accounts for urea formation, while *NO intermediates promote methanol production. This study not only provides a new electrocatalyst for highly efficient urea and methanol electrosynthesis but also can guide the design of other electrocatalysts for high‐value chemicals.