Interfacial Electric Field Sharping by Non‐Ionic Halogens Enables Selective CO 2 ‐to C 2+ Electroreduction

ABSTRACT Halide ions are widely employed to accelerate the electrochemical CO 2 reduction reaction (CO 2 RR), but their practical application is hampered by site blocking and electrode corrosion. Here we present an organic‐inorganic hybrid (OIH) strategy that embeds non‐ionic halogenated molecules (C 8 H 17 X, X = Cl, Br, I) into the Cu 2 O matrix to shape interfacial electric fields. This design preserves the kinetic benefits of halides while eliminating instability from ionic incorporation. The optimized C 8 H 17 Cl‐Cu 2 O OIHs delivers an outstanding C 2+ Faradaic efficiency of 80.6% with a partial current density of 161.2 mA cm −2 . Spectroscopic and theoretical analyses reveal that non‐ionic halogens act as molecular “field shapers,” generating strong interfacial electric fields that strengthen *CO adsorption and balance atop/bridge configurations. This tailored *CO landscape promotes efficient C–C coupling by simultaneously increasing coverage and dimerization kinetics. Our findings establish non‐ionic halogen modifiers as a robust platform for stabilizing and steering interfacial electric fields in CO 2 RR, offering a general strategy for designing selective and durable electrocatalysts.