LAUSR

High‐rate conversion of carbon dioxide (CO2) to ethylene (C2H4) in the CO2 reduction reaction (CO2RR) requires fine control over the phase boundary of the gas diffusion electrode (GDE) to overcome the limit of CO2 solubility in aqueous electrolytes. Here, a metal–organic framework (MOF)‐functionalized GDE design is presented, based on a catalysts:MOFs:hydrophobic substrate materials layered architecture, that leads to high‐rate and selective C2H4 production in flow cells and membrane electrode assembly (MEA) electrolyzers. It is found that using electroanalysis and operando X‐ray absorption spectroscopy (XAS), MOF‐induced organic layers in GDEs augment the local CO2 concentration near the active sites of the Cu catalysts. MOFs with different CO2 adsorption abilities are used, and the stacking ordering of MOFs in the GDE is varied. While sputtering Cu on poly(tetrafluoroethylene) (PTFE) (Cu/PTFE) exhibits 43% C2H4 Faradaic efficiency (FE) at a current density of 200 mA cm−2 in a flow cell, 49% C2H4 FE at 1 A cm−2 is achieved on MOF‐augmented GDEs in CO2RR. MOF‐augmented GDEs are further evaluated in an MEA electrolyzer, achieving a C2H4 partial current density of 220 mA cm−2 for CO2RR and 121 mA cm−2 for the carbon monoxide reduction reaction (CORR), representing 2.7‐fold and 15‐fold improvement in C2H4 production rate, compared to those obtained on bare Cu/PTFE.