It is demonstrated by cyclovoltammetry and ESR spectroscopy that N,N,N,’N,’-tetramethyl; tetraethgl, tetra-n-propyl, tetra-n-butyl-p-phenylenediamine and tetraethyl, tetra-n-propyl-p-benzidine undergo deprotonat ion and two consecutive single electron transfer step CE reaction at electrode in aqueous acetonitrile with the corresponding radical cations as the intermediate. The bivalent cations produced at the electrode react not only with hydroxyl anion in the medium to give quinone but also with the N-alkyl-p-phenylene-diamines or benzidines to produce the corresponding radical cations. It is demonstrated by cyclovoltammetry and ESR spectroscopy that N, N, N, ’N,’ - tetramethyl; tetraethgl, tetra-n-propyl, tetra-n-butyl- p-phenylenediamine and tetraethyl, tetra-n-propyl- benzidine undergo deprotonat ion and two consecutive single electron transfer step CE reaction at electrode in aqueous acetonitrile with the corresponding radical cations as the intermediate. The bivalent cations produced at the electrode react not only with hydroxyl anion in the medium to give quinone but also with the N-alkyl-p-phenylene-diamines or benzidines to produce the corresponding radical cations.