The peroxo-polytungstic acid was formed by the direct reaction of tungsten powder with the hydrogen peroxide solution. Peroxo-polytungstic powder were prepared by rotary evaporator using the fabricated on to ITO coated glass as substrate by dip-coating method using 2g/10mL(W-IPA/H₂O) sol solution. A substrate was dipped into the sol solution and after a meniscus had settled, the substrate was withdrawn at a constant rate of the 3mm/sec. Thicker layer could be built up by repeated dipping/post-treatment 15 times cycles. The layers dried at the temperature of 65∼70℃ during the withdrawn process, and then tungsten oxides thin film was formed by final heating treatment at the temperature of 230∼240℃ for 30min. A linear rotation between the thickness of thin film and the number of dipping/post-treatment cycles for tungsten oxides thin films made by dip-coating was found. The thickness of thin film had 60 Å after one dipping. From the patterns of XRD, the structure of tungsten oxides thin film identified as amorphous one and from the photographs of SEM, the defects and the moderate cracks were observed on the tungsten oxides thin film, but the homogeneous surface of thin films were mostly appeared. The electrochemical characteristic of the ITO/WO₃ thin film electrode were confirmed by the cyclic voltammetry and the cathodic Tafel polaization method. The coloring bleaching processes were clearly repeated up to several hundreds cycles by multiple cyclic voltammetry, but the dissolved phenomenon of thin film revealed in H₂SO₄ solution was observed due to the decrease of the current densities. The diffusion coefficient was calculated from irreversible Randles-Sevick equation from the data obtained by the cyclic voltammetry with various scan rates.