ZIF-8 nanoparticle-doped polyvinyl alcohol (PVA)-S-MC films were prepared via casting method. The effect of different concentrations of ZIF-8 on the physical properties and structural characterization of the films were investigated. The results indicated that ZIF-8 could increase the water resistance and mechanical property of the membrane. Through FTIR, scanning electron microscope (SEM), atomic force microscope (AFM), and TGA analysis, it was found that ZIF-8 changed the phenomenon of macromolecule agglomeration and improved the thermal stability of the membrane. The breathable behavior of the film was also studied through oxygen permeability and water vapor permeability analysis. The result illustrated that the breathability of the film improved significantly by adding ZIF-8. The maximum reached when the weight ratio of ZIF-8 was 0.01 wt %. The property expands the application of PVA/starch blend film in the postharvest technology of fruits and vegetables.