Electrochemical oxidation of intramolecular charge transfer complexes (ICTs) derived from 1,4-naphthoquinone has been studied in acetonitrile using cyclic voltammetry and RRDE. The anodic oxidation of 2-substituted 3-arylamino-1,4-naphthoquinone autocomplexes AC I proceeds in one quasi-reversible stage. The ICT conformation is preserved not only during the electron transfer, but also in the cation radicals formed. The results, obtained from electro-oxidation of AC, confirm the marked electron acceptor properties of the arylamino moiety, at the same time acting as an electron donor in the intramolecular donor-acceptor (D-A) bond. A relationship between redox potentials and ICT electron transfer energy has been found in the case of AC I reversible electrochemical redox reactions.