Regulating Interfacial Hydrogen‐Bonding Networks by Implanting Cu Sites with Perfluorooctane to Accelerate CO2 Electroreduction to Ethanol

Efficient CO2 electroreduction (CO2RR) to ethanol holds promise to generate value‐added chemicals and harness renewable energy simultaneously. Yet, it remains an ongoing challenge due to the competition with thermodynamically more preferred ethylene production. Herein, we presented a CO2 reduction predilection switch from ethylene to ethanol (ethanol‐to‐ethylene ratio of ~5.4) by inherently implanting Cu sites with perfluorooctane to create interfacial non‐covalent interactions. The 1.83%F‐Cu2O organic‐inorganic hybrids (OIHs) exhibited an extraordinary ethanol faradaic efficiency (FEethanol) of ∼55.2%, with an impressive ethanol partial current density of 166 mA cm‐2 and excellent robustness over 60 hours of continuous operation. This exceptional performance ranks our 1.83%F‐Cu2O OIHs among the best‐performing ethanol‐oriented CO2RR electrocatalysts. Our findings identified that C8F18 could strengthen the interfacial hydrogen bonding connectivity, which consequently promotes the generation of active hydrogen species and preferentially favors the hydrogenation of *CHCOH to *CHCHOH, thus switching the reaction from ethylene‐preferred to ethanol‐oriented. The presented investigations highlight opportunities for using noncovalent interactions to tune the selectivity of CO2 electroreduction to ethanol, bringing it closer to practical implementation requirements.