Deposition of tungsten trioxide, WO3, thin films on c-Si substrates by sol-gel technique using a precursor based on non-alkoxide materials has been done in this study. Differential scanning calorimetry, DSC, thermogravimetry, TGA, and differential thermal analysis, DTA, have been used to monitor structural changes during heating. Thermal analysis of the xerogel gives a clear idea about water evolving and phase change. X-ray diffraction, XRD, investigations revealed that the film dried at 120 ˚C for 1h is amorphous. After annealing at 700˚C for 2h, a monoclinic phase of WO3 with preferred orientation along (200) direction appeared. Chemical bonding has been explored by Fourier transform infrared spectroscopy, FTIR. Surface roughness has been found to increase with the increase of annealing temperature as revealed from AFM measurements. At temperatures equal and above 700 ˚C, contact angle decreased due to surface roughness increase. Correlation between the characteristic properties and the contact angle measurements has been discussed.