Tungsten trioxide (WO(3)) electrochromic coatings have been formed on indium tin oxide-coated glass substrates by aqueous routes. Coating sols are obtained by dissolving tungsten powder in acetylated (APTA) or plain peroxotungstic acid (PTA) solutions. The structural evolution and electrochromic performance of the coatings as a function of calcination temperature (250 degrees C and 400 degrees C) have been reported. Differential scanning calorimetry and X-ray diffraction have shown that amorphous WO(3) films are formed after calcination at 250 degrees C for both processing routes: however, the coatings that calcined at 400 degrees C were crystalline in both cases. The calcination temperature-dependent crystallinity of the coatings results in differences in optical properties of the coatings. Higher coloration efficiencies can be achieved with amorphous coatings than could be seen in the crystalline coatings. The transmittance values (at 800 nm) in the colored state are 35% and 56% for 250 degrees C and 400 degrees C-calcined coatings, respectively. The electrochemical properties are more significantly influenced by the method of sol preparation. The ion storage capacities designating the electrochemical properties are found in the range of 1.62-2.74 x 10(-3) (mC cm(-2)) for APTA coatings; and 0.35-1.62 x 10(-3) (mC cm(-2)) for PTA coatings. As a result, a correlation between the microstructure and the electrochromic performance has been established. (C) 2009 Elsevier B.V. All rights reserved.