The objective of this study was to develop and characterize chitosan-ε-polycaprolactone (CHI/PCL) polymer blends with Tween 80 as a compatibilizer for application in packaging. The blends were produced by casting, with up to 10% (w/w) PCL in the CHI matrix. These blends were characterized in terms of their microstructure, chemical interactions, mechanical and thermal properties, solubility and water vapor permeability (WVP). The micrographs showed microsphere-like structures from the PCL in the continuous phase of CHI. Fourier transform infrared spectroscopy (FTIR) indicated a high interaction between CHI amino groups and PCL carbonyls, resulting in blends with greater ductility than the pure CHI film, thus providing greater flexibility. In the crystallinity analyses, the presence of PCL favored an increase in crystalline regions, limiting the passage of light. Given the results, blends are an alternative for application in multilayer systems and can be considered for use as a biodegradable fraction in food packaging.