A regioselective synthesis of N,N′-diphenyl-3-sulfonyl-[1,1′- biphenyl]-4,4′-diamine derivatives is carried out by anodic oxidation of N,N′-diphenylbenzidine in the presence of sulfinic acids as nucleophiles via a convergent paired electrochemical process. The sulfonylated aromatic amine products are obtained under mild reaction conditions with high yields, high current efficiency and atom economy.