Benzothiazolylsulfenamides are prepared in a high yield and substantially without a side reaction, via direct electrolytic oxidation, by cross-coupling (1) 2-mercaptobenzothiazole or dibenzothiazyl disulfide or an alkali metal salt of 2-mercaptobenzothiazole with (2) a primary or secondary amine, in the presence of a solvent selected from a dipolar aprotic solvent, a protic solvent, water and mixtures thereof, as well as a supporting electrolyte having adaptability to the solvent.