In conclusion, we have reported a mechanism by which AC electrolysis controls the one-or two-electron oxidation of amines to amino radicals or iminium cations, enabling selective α-amine functionalization by adjusting the AC frequency. We found that the selective one-electron oxidation of amines to amino radicals was achieved by providing a reducing environment for the deprotonation of amino radical cations. We have also developed a convenient electroanalytical method to identify the optimal AC frequency that maximizes the arylation product of the one-electron oxidation pathway, eliminating the time-consuming trial-and-error approach in conventional AC electrolysis condition optimization. We envision that this highly efficient and unique AC electrolysis protocol can be applied to achieve unique reactivities in synthetic and medicinal chemistry.