In summary, we present a system comprised of a molecular Co Terpy-RF catalyst that assembles via hydrophobic interactions through perfluorinated side chains. The hydrophobicity was leveraged to integrate these species into a GDE in which the hydrophobicity is an inherent advantage rather than obstacle. The unique reaction environment within these Co Terpy-RF layers shifted the CO2R selectivity to CH4, which reached up to 80% in an optimized system. Mechanistic investigations suggest that the hydrophobic catalytic pocket stabilizes CO2R intermediates while a pyridine-assisted proton conduit acts to shuttle protons to the active sites and hydrogenate the intermediates en route to the CH4 final product. These findings pave the way towards the use of functional catalytic environments that dictate electrocatalytic behaviour and enable access to new reactivity.