Cyclic voltammetry was used to investigate the electrochemical behaviour of the tungsten oxide films toward the electroreduction of BrO3- ClO2- and NO2- ions in acidic medium. The effects of the temperature, scan rate, pH, chemical composition of the electrolytic solutions, were investigated and the reduction mechanism was critically discussed. The reduction currents, evaluated in cyclic voltammetry and measured at -0.250 V versus SCE, increased linearly on increasing analyte concentration up to 20, 55 and 45 mM for nitrite, chlorite and bromate ions, respectively. The detection limits, evaluated in cyclic voltammetry, were 0.1, 0.4 and 0.7 mM for BrO3-, ClO2- and NO2-, respectively. The tungsten oxide film was successfully characterized as an amperometric sensor for the analytical determination of BrO3- ClO2- and NO2- ions in flowing stream. Operating under constant applied potential of -0.3 V versus Ag/AgCl the good reproducibility of the peak height and background current level during consecutive injections, indicates the absence of fouling effects and the potential applicability of the amperometric sensor for the routine analytical determination of the investigated inorganic ions. Considering the low values of the background currents (ca. 1.1 +/- 0.1 mu A) obtained in acidic and not deoxygenated carrier electrolyte, the tungsten sensing electrode seems to compete favourably with other common sensors for the amperometric determination of electroactive molecules under cathodic conditions. The X-ray photoelectron spectroscopy technique (XPS) was used in order to evaluate the chemical composition of the tungsten film upon electrochemical treatment in 0.1 M H2SO4 Solution. Independently of the electrochemical treatment in acid solution, the tungsten surface electrode is generally composed by 50-60% of W-0, 35-40% of W6+ and traces of W2+ oxide species. (c) 2005 Elsevier Ltd. All rights reserved.