Orthogonal Control of Lattice Oxygen Activation and Oxygen Evolution Reaction Suppression via “Molecular Gates” for High‐Efficiency Nitrile Electrosynthesis

A fundamental barrier to industrial electrosynthesis is the inescapable trade‐off between activity and selectivity at high current densities, where parasitic reactions overwhelm the desired interfacial chemistry. Here, we introduce a bioinspired interfacial decoupling strategy using hexamethylphosphoramide (HMPA) to resolve this challenge for nitrile electrosysthesis. The activation of lattice oxygen for substrate dehydrogenation via metal‐ligand charge redistribution, and the suppression of OH − ‐driven oxygen evolution reaction (OER) via electrostatic shielding by hydrophobic alkyl chains are concurrently controlled. As a result, we achieved simultaneously high activity (1.37 V @300 mA cm −2 ), near‐unity selectivity (93.3% Faradaic efficiency (FE)), and pharmaceutical‐grade purity for propionitrile production. Further reinforced by exceptional stability (>300 h at industrially relevant current densities), a record production rate (143.86 mg cm −2 h −1 ), and ∼30% energy reduction, the system significantly outperforms state‐of‐the‐art benchmarks. Furthermore, this electrolyte‐catalyst co‐optimization strategy proves universal across primary/secondary amines, offering a blueprint for sustainable chemical manufacturing beyond fossil‐fueled processes.