The electro-oxidation of naphtho[1,8-cd][1,2]dithiole (DTN) in acetonitrile (AN) solution led to the formation of a blue-violet, air-stable, polymeric film (poly(DTN)) on glassy carbon (GC) and platinum (Pt) electrodes. The film demonstrated reversible, well-defined oxidation-reduction responses having multiple redox potential in a range of 0.00 to + 1.20 V vs. Ag wire quasi-reference electrode (Ag(QRE)) in aprotic non-aqueous solutions. The structures of electroactive moieties of poly(DTN) like a conjugated polymer at the oxidation-state are proposed. The reaction mechanism for the initial (especially dimer formation) stages of the electropolymerization of DTN was also estimated. (C) 2010 Elsevier B.V. All rights reserved.