Tungsten trioxide (WO3) thin films were prepared by thermal evaporation technique on thoroughly cleaned glass substrates at high pressure of 133.322 mPa in presence of argon. The substrate temperature was maintained from 6 °C to 8 °C with the help of a cold jar. The deposited films were annealed at 400 °C in air for about 2 hours. The films were characterized in terms of their composition by X-ray photoelectron spectroscopy. Subsequently, the laboratory developed dry lithiation method was used to intercalate lithium atoms into as-deposited films in various proportions. With the amount of lithium content inserted into the film, the films showed coloration in visible and near infrared regions. The morphology, coloration efficiency and optical constants of annealed and lithiated films were calculated.