Electrochemical investigations (polarography, cyclic voltammetry, rotating ring-disk electrode voltammetry) of intramolecular charge transfer complexes (AC) derived from 1,4-naphthoquinone were performed in acetonitrile. It is concluded that in the first one-electron stage of its electrochemical reduction the AC is in a complexed form. At the same time the amino moiety, which shows a marked inductive (−I) effect, acts as an electron donor in the donor-acceptor (D-A) interaction. Facilitation of the reduction of the quinone part by the aryl amine residue is compensated by the D-A interaction, which makes the electroreduction more difficult. By using ultramicroelectrodes it was shown that the primary reaction products (naphthosemiquinone anions) easily form ion pairs with the tetrabutylammonium ion (TBA⁺).