Electrochemical and spectroscopic (EPR, UV–Vis, IR) studies of the aromatic secondary amines N, N′-diphenyl-1,4-phenylenediamine (DPPD), N-phenyl- N′-isopropyl- p-phenylene diamine (IPPD), N-phenyl- N′-(α-methylbenzyl)- p-phenylenediamine (SPPD) and N-phenyl- N′-(1,3-dimethyl-butyl)- p-phenylenediamine (6PPD), which represent the most important group of antioxidants used in the rubber industry, are presented. During oxidation, all the compounds show reversible redox couples in acetonitrile/0.1 M TBABF 4. The first oxidation potential depends substantially on the R substituent at the –N′H– moiety. Very similar UV–VIS spectra of monocation radicals and dications for all the compounds were observed by applying anodic oxidation as well as oxidation by tert-butyl hydroperoxide both in air and in inert atmosphere. The samples with N′-bonded aliphatic carbon in the molecule (e.g. IPPD) heated in air undergo consecutive chemical reactions leading to the formation of –N′ C– group. By the use of RO 2 radicals only very low concentration of nitroxide radicals was obtained. Very high concentration of nitroxide radicals was achieved using 3-chloroperbenzoic acid. In the oxidation of investigated aromatic secondary amines with powder PbO 2 no EPR spectra were observed and UV–Vis and IR studies indicate the rapid formation of the final dehydrogenated oxidation product.