A series of 1, 4-dichloroazoethanes (1-X/Y, X and Y= 4-NO2, 4-CN, 4-CH3 or 4-H) were studied in N, N-dimethylformamide using cyclic voltammetry, constant potential sweep voltammetry (CPSW) and constant potential electrolysis. The voltammograms of 1-X/Y exhibit an irreversible two-electron wave corresponding to dissociative electron transfer (DET) reduction of the carbon–chlorine bond resulting in formation of the azines 2-X/Y in ...