Amongst various sol-gel routes to deposit large area WO3 films for electrochromic applications, the one using peroxotungstic acid based precursor solution gives superior electrochromic films. Further improvements in the properties are possible by chemical modification of the precursor material and by controlling the post deposition thermal treatment. Both these parameters affect physical, structural, electrical and as a result electrochromic properties of the films significantly. A detailed study of these properties of the films deposited with precursor solution modified with various organic additives and different thermal parameters was undertaken. X-ray diffraction, electron microscopy and resistance measurements were used to characterize and compare the films. These properties of the films correlated to their electrochromic behavior are reported in this paper.