Starch is a biopolymer with enormous potential for generating new biodegradable packages due to its easy availability and low cost. However, due to its weak functional properties, limitation of its interaction with some hydroxyl groups and evaluation of blends with other polymers are necessary in order to improve its performance. Glycerol-plasticized acetylated corn starch films were developed using the casting method, and the impact of incorporating chitosan (TPS:CH) in various proportions (75:25, 50:50, and 25:75 /) was studied in the present research. The effect of chitosan ratios on the physical, mechanical, water-vapor barrier, and thermal properties of the film was studied. Chitosan-protonated amino groups promoted the formation of intermolecular bonds, improving tensile strength, thermal stability, hydrophobicity, water adsorption capacity, and the gas barrier of starch films. The results show that the film composed of TPS25-CH75 proved to be the best barrier to water vapor; thus, these composite films are excellent choices for developing biodegradable packaging for the food industry.