Interface‐Regulated Orbital Coupling Enables Nucleophilic Carbon Assembly Pathways in Electrochemical CO ₂ Conversion

Abstract Achieving selective and durable CO 2 electroreduction to ethanol remains challenging due to the instability of Cu oxidation states and inefficient C─C coupling. Here, we construct a Zn single‐atom‐Cu 2 O hybrid catalyst, where atomically dispersed Zn atoms form a well‐defined ZnO─Cu interface. The catalyst delivers a high ethanol Faradaic efficiency of 74.4% and operates stably for 200 h. Density functional theory and operando X‐ray absorption spectroscopy reveal that an intrinsic orbital coupling between Zn4 s/4p and O 2p orbitals induces interfacial polarization. Under reaction conditions, this polarization stabilizes low‐coordinated Cu⁺ sites and facilitates *CHO formation. This polarization enables a nucleophilic C─C coupling pathway that bypasses *CO dimerization, reducing the kinetic barrier for ethanol formation. The concept of interfacial orbital regulation demonstrated here provides a general strategy for steering multi‐electron reactions and C─X bond formation in electrochemical carbon valorization.