In this work, we demonstrate for the first time the deliberate integration of hydrophobicity into a molecular CO2R catalyst operating at the gas-liquid-solid interface within a gas-diffusion electrode (Fig. ). Our system consists of Co terpyridine catalysts with perfluorinated alkyl chains (Co Terpy-RF) that render the system hydrophobic due to the perfluoro-perfluoro interactions between the perfluorinated alkyl chains (Fig. ). To our surprise, the Co Terpy-RF system was found to be selective for methane production, a stark contrast to other Co-pyridine catalysts that primarily produced CO or formate. A gamut of mechanistic investigations provided evidence that the catalysts operated within a hydrophobic catalytic pocket through which protons were shuttled via a pyridine ligand centered conduit. This unique environment altered the selectivity from CO to CH4, with an optimized system featuring Faradaic efficiency (FE) above 80% at 10 mA cm -2 , a first for molecular CO2R systems.