The majority of food packaging materials are petroleum-based polymers, which are neither easily recyclable nor ecologically friendly. Packaging films should preferably be transparent, light in weight, and easy to process, as well as mechanically flexible, and they should meet the criteria for food encapsulation. In this study, poly (vinyl alcohol) (PVA)-based films were developed by incorporating glass flakes into the films. The selection of PVA was based on its well-known biodegradability, whereas the selection of glass flakes was based on their natural impermeability to oxygen and moisture. The films were processed using the blade coating method and were characterized in terms of transparency, oxygen transmission rate, mechanical strength, and flexibility. We observed that the incorporation of glass flakes into the PVA matrix did not significantly change the transparency of the PVA films, and they exhibited a total transmittance of around 87% (at 550 nm). When the glass flakes were added to the PVA, a significant reduction in moisture permeation was observed. This reduction was also supported and proven by Bhardwaj’s permeability model. In addition, even after the addition of glass flakes to the PVA, the films remained flexible and showed no degradation in terms of the water vapor transmission rate (WVTR), even after bending cycles of 23,000. The PVA film with glass flakes had decent tensile characteristics, i.e., around >50 MPa. Increasing the concentration of glass flakes also increased the hardness of the films. Finally, a piece of bread was packaged in a well-characterized composite film. We observed that the bread packaged in the PVA film with glass flakes did not show any degradation at all, even after 10 days, whereas the bread piece packaged in a commercial polyethylene bag degraded completely. Based on these results, the developed packaging films are the perfect solution to replace commercial non-biodegradable films.