Anodic oxidation of various types of 2-methoxy-2,3,3,3-tetrafluoropropylamines ArRNCH2Y [Y = CF(OMe)CF3] was carried out in KOH/MeOH. Methoxylation alpha to the Y group and/or cleavage of a carbon-nitrogen bond took place depending on the kind of R groups. The regioselectivity of such methoxylation and C-N cleavage can be explained mainly in terms of the alpha-CH kinetic acidities of the cation radicals formed by one-electron oxidation of the amines. Furthermore, reasonable diastereoselectivity was obtained in the anodic methoxylation when the R group is alkyl. On the other hand, when the R group is aryl, the diastereoselectivity was extremely low.