We report a surfactant-free exfoliation method of WS2 flakes combined with a vacuum filtration method to fabricate thin (<50 nm) WS2 films, that can be transferred on any arbitrary substrate. Films are composed of thin (<4 nm) single flakes, forming a large size uniform film, verified by AFM and SEM. Using statistical phonons investigation, we demonstrate structural quality and uniformity of the film sample and we provide first-order temperature coefficient χ, which shows linear dependence over 300–450 K temperature range. Electrical measurements show film sheet resistance RS = 48 MΩ/Υ and also reveal two energy band gaps related to the intrinsic architecture of the thin film. Finally, we show that optical transmission/absorption is rich above the bandgap exhibiting several excitonic resonances, and nearly feature-less below the bandgap.