Constructing Ag/Cu2O Interface for Efficient Neutral CO2 Electroreduction to C2H4

Neutral CO2 electroreduction to multi‐carbons (C2+) offers a promising pathway to reduce the CO2 and energy losses originating from the carbonate formation. However, the sluggish kinetics of C−C coupling brings a significant challenge of achieving high selectivity of a single product (such as ethylene), especially at industrial‐relevant current densities (>300 mA cm−2). Here, we reported an optimized Ag‐Cu2O interfacial catalyst that exhibited C2+ Faradaic efficiency (FE) of 73.6 % at 650 mA cm−2 in a flow cell. Remarkably, it obtained FEC2H4 of 66.0 % with a partial current density of 429.1 mA cm−2, making it stand out among the reported Cu‐based electrocatalysts. In situ Raman spectra uncovered that the Ag/Cu2O interfaces enabled a high coverage of *CO around the partially reduced Cu+/Cu0 active sites. Furthermore, theoretical calculations demonstrated the enhanced CO formation and C−C coupling at the Ag/Cu2O interface. This work reported an unprecedented neutral CO2 electroreduction to C2H4 performance and provided an in‐depth comprehension of the role of the bimetallic interface. Construction of Ag/Cu2O interface significantly enhanced the C2H4 partial current density from 250.9 (Cu2O) to 429.1 mA cm−2 in the neutral electrocatalytic CO2RR, showing a great breakthrough in activity and selectivity toward single products. Analytical results reveal partially preserved Cu+ species and increased CO coverage at interface synergistically promote C−C coupling, which enhances the understanding of bimetallic interface functions.