AbstractDeveloping highly efficient and selective electrocatalysts for the CO2 reduction reaction to produce value‐added chemicals has been intensively pursued. We report a series of CuxOyCz nanostructured electrocatalysts derived from a Cu‐based MOF as porous self‐sacrificial template. Blending catalysts with polytetrafluoroethylene (PTFE) on gas diffusion electrodes (GDEs) suppressed the competitive hydrogen evolution reaction. 25 to 50 wt % teflonized GDEs exhibited a Faradaic efficiency of ≈54 % for C2+ products at −80 mA cm−2. The local OH− ions activity of PTFE‐modified GDEs was assessed by means of closely positioning a Pt‐nanoelectrode. A substantial increase in the OH−/H2O activity ratio due to the locally generated OH− ions at increasing current densities was determined irrespective of the PTFE amount.