The pyroligneous liquor is a product obtained during the production of charcoal, with well-known antimicrobial activity. In this work, we characterized the physical chemistry properties of a formulation composed of distilled pyroligneous liquor (DPL), obtained from Eucalyptus grandis, and chitosan. A good interaction between the polymer and the solvent was observed. Auto-supported films were prepared with these systems and characterized with respect to their structure and photo-protection properties, water vapor permeability, and resistance to water and to thermal degradation. They present a semi-crystalline structure and are hygroscopic, but are stable under immersion for up to 7 days. The swelling degree in water is 300% in weight and the permeability to water vapor was between 30 and 45 g m −1 h −1 (for films with 80 to 10 μm, respectively). The obtained films are able to efficiently block the incident UVB and UVC radiation; the molar absorptivity decreases exponentially with increasing wavelength and is stable up to 300°C. These properties confer desirable properties to the films, obtained from these precursors of a renewable source, to be used as coatings.