WO3 films have been prepared on to IrO2-coated Ti substrate by cathodic deposition, and as-deposited and annealed films have been characterized using XRD, TEM, Raman and FT-IR spectroscopy. The as-deposited film consists of nanocrystalline, orthorhombic WO3.H2O and this phase transforms to amorphous WO3 by annealing at 250 degreesC and to monoclinic WO3 by annealing at and above 350 degreesC. The as-deposited and annealed films have been used as anodes for electrochemical decomposition of phenol in aqueous solutions with and without chloride ions. The monoclinic WO3 anodes prepared by annealing at 350 and 400 degreesC show relatively high electrochemical activity in the chloride-containing solution. In addition, the anodes possess high chemical and physical stabilities: very low dissolution rate of WO3 during the electrolysis and good adhesion to the substrate. Thus, WO3 anodes may be promising materials for anodic oxidation of bio-refractory organics in wastewater, although further improvement of electrochemical activity is needed for more effective decrease in total organic carbons in wastewater. (C) 2002 Elsevier Science Ltd. All rights reserved.