Molecular Bridge Enables Dual‐Intermediate Synergy for Selective CO 2 Electroreduction to Multicarbon Products

ABSTRACT CO 2 electroreduction to multicarbon products offers a sustainable pathway for chemical synthesis, yet its practical efficiency has long been hindered by the kinetically mismatched *CO and *H intermediates, a fundamental bottleneck in multicarbon formation. Here, we address this challenge through a new molecular‐bridge‐enabled dual‐intermediate synergy strategy. By integrating sulfonated cobalt phthalocyanine molecules with two‐dimensional Cu nanosheets, we construct a cooperative catalytic interface in which the molecular bridge not only activates CO 2 to generate *CO but also reorganizes the interfacial water network to facilitate proton transfer for *H feeding. This synchronized CO*─H* delivery to the Cu active sites dramatically enhances C─C coupling and subsequent hydrogenation. As a result, the Cu─CS nanosheets achieve 81% Faradaic efficiency for C 2+ products at 400 mA cm −2 and maintain stable operation for > 105 h. Importantly, Cu─CS nanosheets shift the reaction pathway from the CO/H 2 ‐dominated output of pristine Cu nanosheets to a C 2+ ‐selective profile, boosting the C 2+ :(CO + H 2 ) ratio from 0.7 to 4.6, an over sixfold improvement. In situ spectroscopy reveals enriched high‐frequency atop‐bound *CO and increased proton‐transfer‐active 2‐HB·H 2 O species, synergistically accelerating C 2+ intermediate formation and indicating the effectiveness of molecular intermediate synergy in steering electrocatalytic pathways and product distribution.