A carbon paper-based gas diffusion electrode (GDE) is used with a bismuth(III) subcarbonate active catalyst phase for the electrochemical reduction of CO2 in a gas/electrolyte flow-by configuration electrolyser at high current density. It is demonstrated that in this configuration, the gas and catholyte phases recombine to form K2CO3/KHCO3 precipitates to an extent that after electrolyses, vast amount of K+ ions is found by EDX mapping in the entire GDE structure. The fact that the entirety of the GDE gets wetted during electrolysis should, however, not be interpreted as a sign of flooding of the catalyst layer, since electrolyte perspiring through the GDE can largely be removed with the outflow gas, and the efficiency of electrolysis (toward the selective production of formate) can thus be maintained high for several hours. For a full spatial scale quantitative monitoring of electrolyte penetration into the GDE, (relying on K+ ions as tracer) the method of inductively coupled plasma–mass spectrometry (ICP–MS) assisted energy dispersive X-ray (EDX) tomography is introduced. This new, cheap and robust tomography of non-uniform aspect ratio has a large planar span that comprises the entire GDE surface area and a submicrometer depth resolution, hence it can provide quantitative information about the amount and distribution of K+ remnants inside the GDE structure, in three dimensions.