The natural deep eutectic solvent (NADES) based on choline chloride (ChCl) and lactic acid (LA) was used for the preparation of chitosan (CS) films by the solution casting method. The content of NADES in films was from 0 to 82 wt%. The impact of NADES on the morphology and crystalline structure of films was investigated using scanning electron microscopy as well as wide-angle and small-angle X-ray scattering. The experimental results allow to propose CS chains swelling in NADES. FTIR spectroscopy confirms the interactions between CS and NADES components via the formation of hydrogen and ion bonds. The thermal properties of the composite films were studied by simultaneous thermogravimetric and differential thermal analysis. Thermomechanical analysis demonstrated appearance of two transitions at temperatures between −23 and −5 °C and 54–102 °C depending on NADES content. It was found that electrical conductivity of film with 82 wt% of NADES reaches 1.7 mS/cm. The influence of the composition and structure of films on the charge carriers concentration and their mobility is discussed.