Tungsten oxide (WO3) and nano-rod sodium tungstate (Na2W2O7) thin film was prepared by dip coating on slide glass (SG) and tin-doped indium oxide (ITO) coated glass in peroxotungstic acid (PTA) solution. Thermal analysis results showed that PTA is decomposed to tungsten oxide via multiple steps of WO3 center dot 2/3H(2)O, WO3 center dot 1/3H(2)O and WO3. Monoclinic phase appeared on ITO glass at 400 degrees C and crystal growth occurred at 500 degrees C. However, quite different crystallization behavior appeared on SG due to sodium ion diffusion. At 400 degrees C, rectangular shape crystals identified as Na2W4O13 appeared in amorphous matrix, and grew to bundles of rod-shaped Na2W2O7 and Na2W4O13 phase at 500 degrees C. Raman scattering spectroscopy data confirmed the formation of Na2W4O13 and Na2W2O7 at 500 degrees C. The understanding of crystallization behavior and sodium ion diffusion into WO3 thin film on different substrates may be helpful to the application area of electrochromic windows or photocatalyst. (C) 2009 Elsevier B.V. All rights reserved.