Dual Electric Fields Enrich and Stabilize Intermediates for Efficient Electrochemical CO ₂ Reduction to Multi‐Carbon Products

Abstract Electrochemical reduction of CO ₂ , a technology with great potential for renewable energy storage and climate change mitigation, depends on critical C─C coupling steps in CO ₂ RR to ensure efficient high‐value hydrocarbon production. In this work, a local interface electric field and a tip‐induced electric field are constructed on Ag‐embedded Cu nanoneedle arrays to enhance the concentration of the *CO intermediate and regulate the adsorption of key intermediates, respectively. This optimization of the reaction microenvironment promotes the deep reduction of the *CO intermediate into multi‐carbon products (C ₂₊ ), with a faradaic efficiency of 83.7% and a C ₂₊ local current density of −526 mA cm ⁻² within gas‐fed flow cells. Experimental evidence and simulations validate that the interface electric field of the Cu‐Ag bimetallic catalyst increased surface *CO coverage, substantially lowering the formation barrier for *CHO intermediate, and the tip‐induced electric field that can stabilize *CO intermediate and suppress hydrogen evolution, promoting the C─C coupling process. The formation of the dual electric fields profoundly induced local environments and ultimately, the dominant C ₂₊ product, which offers significant design guidelines for adjusting the supply and demand balance of reaction intermediates.