While the appearance of the electrodes under AP conditions remained unaltered, the anode surface of the DC experiment electrodes had clearly been compromised. Moreover, electrode weight was monitored before and after electrolysis, observing non-negligible mass gain only on the DC anode, further supporting irreversible anode fouling. It was reasoned that such anode fouling occurs due to the depletion of oxidizable substance on the anode. This situation is comparable to the rAP-Kolbe reaction, where smooth decarboxylation only under rAP conditions could be explained by a local pH difference around the electrodes. Namely, DC electrolysis generates locally acidic areas around the anode through the formation of electrogenerated acids, which suppresses deprotonation of carboxylic acid, and therefore, decarboxylation. In contrast, polarity switching can partially avert this phenomenon by reversing electrode polarity, thus diminishing the accumulation of acid around the electrode. In order to support this hypothesis, probe 30 bearing an acid-labile silyl ether functionality was introduced into the reactions (Figure , top panel).