With the aim of effectively improving the performance of bio-friendly food packaging and circumventing the hazards associated with petroleum-based plastic food packaging, composite films of corn starch and polyvinyl alcohol were prepared using a new method that involved chemical cross-linking of glutaraldehyde and blending with cinnamon essential oil nanoemulsion (CNE). Glutaraldehyde and CNE enhance the film's network structure by chemical bonding and hydrogen bonding, respectively. This results in improved surface smoothness, mechanical properties, and UV shielding ability of the film. However, the films' surface hydrophilicity increased as a result of CNE, which is harmful for food preservation in high humidity. Overall, glutaraldehyde and CNE have a synergistic effect on some of the properties of the film which is mainly attributed to the films' structure improvement. The films have great potential for preparing flexible and UV-shielding films and offer new ideas for developing biodegradable films.