A novel conducting polymer of polynaphthidine, poly(NAP), was synthesized electrochemically by direct anodic oxidation of naphthidine in aqueous media. The yield of the electropolymerization reaction depends on the temperature and pH of the solution. It was possible to differentiate two working regions: 1 (for pH < 0.5 and all temperatures) where the film yield tends to zero and II (for approximately 2.0 < pH < 2.8 and temperatures > 15 degrees C) where the him production is maximum. Therefore, the naphthidine electrooxidation mechanism was studied under experimental conditions of region I by cyclic (CV) and square wave voltammetries (SWV) as well as by controlled potential electrolysis. The experimental conditions of region II were chosen to obtain the poly(NAP). The electrochemical response of the film was investigated in pH 1 HClO4 + 0.1 M NaClO4 electrolyte solution by CV and SWV. A plot of I-p.n/f vs. f from SW voltammograms showed the so-called "quasi-reversible maximum". Formal potential, formal rate Constant and anodic transfer coefficient for the surface redox process were also evaluated from the SWV. The poly(NAP) is insoluble in common organic solvents and shows electrochromic behaviour. its probable structure was determined by FTIR spectroscopy. (C) 2008 Elsevier Ltd. All rights reserved.