Photodegradation and oxidation are major causes of the deterioration of food, resulting in darkening, off-flavors, and nutrient deficiency. To reduce this problem, novel functional polymeric materials are being developed to retain food’s light sensitivity. Nanofillers are also used in a polymeric film to produce effective UV blockings and oxygen barrier coatings so that the degradation of the food can be delayed, thereby increasing the shelf life. For this purpose, polyvinyl alcohol coatings were prepared by the incorporation of ZnO nanoparticles. Polyvinyl alcohol is a naturally excellent barrier against oxygen, and the addition of ZnO particles at the nanoscale size has demonstrated effective UV blocking capabilities. In this work, the hydrothermal technique is used to produce ZnO nanoparticles, and these produced particles are then incorporated into the polyvinyl alcohol to produce thin films. These films are characterized in terms of the compositional, macroscopic, microscopic, and optical properties via X-ray diffraction (XRD), FTIR, scanning electron microscopy (SEM), and thermogravimetric analysis (TGA), as well as UV–VIS spectroscopy. ZnO nanoparticles at different concentrations were incorporated into the PVA solution, and the films were processed via the blade coating method. With the addition of ZnO, the oxygen transmission rate (OTR) of pure PVA was not altered and remained stable, and the lowest OTR was recorded as 0.65 cm³/m²·day·bar. Furthermore, the addition of ZnO increased the water contact angle (WCA) of PVA, and the highest WCA was recorded to be around more than 70°. Due to this, water permeability decreased. Additionally, PVA/ZnO films were highly flexible and bendable and maintained the OTR even after going through bending cycles of 20K. Furthermore, the addition of ZnO showed a significant UV blocking effect and blocked the rays below a wavelength of 380 nm. Finally, the optimized films were used for packaging applications, and it was observed that the packaged apple remained fresh and unoxidized for a longer period as compared with the piece of apple without packaging. Thus, based on these results, the PVA/ZnO films are ideally suited for packaging purposes and can effectively enhance the shelf life of food.