The inevitable two-electron oxidation of amine 1 to iminium 5 and the consequent formation of cyanation product 1b during DC electrolysis can be explained by the cyclic voltammograms (CVs) of 1 collected in the absence and presence of the base, NaOAc, in Figure . Without NaOAc, the CV of 1(red curve) clearly shows two well-separated anodic peaks. The peak at E1=~0.3 V vs. Ag/Ag + belongs to the reversible single-electron oxidation of amine 1 to its corresponding cation radical 3, and the other one at E2 = ~0.9 V arises from the further oxidation of 3 to 5 by another electron. However, when NaOAc was added, the anodic peak at 0.9 V shifted negatively and merged with the 0.3 V peak (black curve), indicating that one-and two-electron oxidation of 1 can take place under similar potentials. The drastically lowered potential for the second-electron oxidation of 1 in the presence of NaOAc is because iminium cations are generated via the low-potential α-amine radical route (E3 < E2, Figure ). As a result, the arylation product 1a is always accompanied by the cyanation product 1b under DC electrolysis, regardless of the applied voltage. Next, we tested AC electrolysis for its effect on product selectivity. During AC electrolysis, oxidation of 1 and reduction of 2 occurred sequentially at the same electrode driven by the alternating voltage polarity. Other reaction conditions, including electrodes, electrolytes, and chemical reagents, were identical to the DC electrolysis conditions (Figure ). We applied sine waveforms with a frequency from 1 Hz to 30 Hz at a fixed AC peak amplitude of 2.5 V. This amplitude was calculated from the potential difference between the oxidation peak of 1 (0.28 V) and the reduction peak of 2 (-2.22V) in the CVs after iR drop correction (Fig- ). Figure shows the product yields and selectivity for DC and AC electrolysis. All AC experiments exhibited a higher selectivity toward the one-electron oxidation pathway (arylation) product 1a than DC electrolysis, meaning a reduced degree of amine oxidation. At 10 Hz, we observed the maximum yield of 68% for 1a and the biggest six-fold selectivity improvement toward 1a over DC electrolysis (1a: 1b = 4.3 vs. 0.7).