In this study, our model reaction is the α-amino C-H arylation reaction, which was first discovered by MacMillan and co-workers using the strategy of accelerated serendipity. This reaction was initially accomplished by photoredox catalysis. We selected this model reaction for two reasons. First, it can be completed by electrochemically oxidizing amine 1 to amine radical cation 3 and reducing 1,4-dicyanobenzene 2 to the corresponding arene radical anion 6 at electrodes (rather than via SET with a photoredox catalyst). The C-H bonds adjacent to the nitrogen atom in 3 are weakened and undergo deprotonation by a base, B -such as NaOAc, to give α-amino radical 4. A radical-radical coupling reaction between intermediates 4 and 6 yields the aromatized benzylic amine product 1a after elimination of CN - (one-electron oxidation (arylation) pathway in Figure ). Second, unlikely photoredox catalysis, electrosynthesis produces a significant amount of cyanation byproduct 1b because of the overoxidation of 1 to iminium cation 5 (the two-electron oxidation (cyanation) pathway in Figure ), enabling us to study how AC electrolysis alters the degree of amine oxidation and controls product selectivity.