Starch is a biopolymer with wide potential for the generation of new biodegradable packages due to its high availability and low price. However, due to its weak functional properties, it is necessary to limit the interaction of some hydroxyl, and to evaluate blends with other polymers to improve their performance. Glycerol plasticized acetylated corn starch films were developed by the casting method, and the impact of incorporating chitosan (TPS:CH) at various proportions (75:25, 50:50, and 25:75 v/v) was studied. The effect of the chitosan ratios on the films' physical, mechanical, water vapor barrier, and thermal properties was evaluated. Chitosan protonated amino groups promote the formation of intermolecular bonds, improving the tensile strength, the thermal stability, the water adsorption capacity, and the gas barrier of starch films. Where the film composed of TPS25-CH75 was the one that presented the best barrier to water vapor. These composite films are a good option for development of biodegradable packaging.