Starch and chitosan are widely used for preparation of edible films that are of great interest in food preservation. This work was aimed to analyze the relationship between structural and physical properties of edible films based on a mixture of chitosan and modified starches. In addition, films were tested for antimicrobial activity against Listeria innocua. Films were prepared by the casting method using chitosan (CT), waxy (WS), oxidized (OS) and acetylated (AS) corn starches and their mixtures. The CT-starches films showed improved barrier and mechanical properties as compared with those made from individual components, CT-OS film presented the lowest thickness (74 ± 7 µm), water content (11.53% ± 0.85%, w/w), solubility (26.77% ± 1.40%, w/v) and water vapor permeability ((1.18 ± 0.48) × 10−9 g·s−1·m−1·Pa−1). This film showed low hardness (2.30 ± 0.19 MPa), low surface roughness (Rq = 3.20 ± 0.41 nm) and was the most elastic (Young’s modulus = 0.11 ± 0.06 GPa). In addition, films made from CT-starches mixtures reduced CT antimicrobial activity against L. innocua, depending on the type of modified starch. This was attributed to interactions between acetyl groups of AS with the carbonyl and amino groups of CT, leaving CT with less positive charge. Interaction of the pyranose ring of OS with CT led to increased OH groups that upon interaction with amino groups, decreased the positive charge of CT, and this effect is responsible for the reduced antimicrobial activity. It was found that the type of starch modification influenced interactions with chitosan, leading to different films properties.