Electrolysis offers an attractive route to upgrade greenhouse gases such as carbon dioxide (CO 2) to valuable fuels and feedstocks; however, productivity is often limited by gas diffusion through a liquid electrolyte to the surface of the catalyst. Here, we present a catalyst:ionomer bulk heterojunction (CIBH) architecture that decouples gas, ion, and electron transport. The CIBH comprises a metal and a superfine ionomer layer with hydrophobic and hydrophilic functionalities that extend gas and ion transport from tens of nanometers to the micrometer scale. By applying this design strategy, we achieved CO 2 electroreduction on copper in 7 M potassium hydroxide electrolyte (pH ≈ 15) with an ethylene partial current density of 1.3 amperes per square centimeter at 45% cathodic energy efficiency.