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Packaging materials based on biodegradable polymers are a viable alternative to replace conventional plastic packaging from fossil origin. The type of plasticizer used in these materials affects their functionality and performance. The effect of different plasticizers such as glycerol (GLY), sorbitol (SOR), and poly(ethylene glycol) (PEG) in concentrations of 5%, 10%, and 15% ( w / w ) on the structural features and functional properties of starch/PVOH/chitosan films was evaluated. The incorporation of a plasticizer increased the thickness of the biodegradable composite films. Furthermore, the material plasticized with 30% ( w / w ) sorbitol had the highest elongation at break, lowest water vapor permeability, and better thermal resistance. The results obtained in this study suggest that maize starch/PVOH/chitosan biodegradable composite films are a promising packaging material, and that sorbitol is the most suitable plasticizer for this formulation.