Hybrid environmentally friendly nanocomposite films were synthesized via electrospinning using polycaprolactone (PCL) and chitosan (CH). The resulting nanofiber films displayed a homogeneous fibrous microstructure with average diameters between 250-270 nm. Molecular simulation experiments revealed a progressive increase in hydrogen bonding over time. The impact of different CH concentrations on surface roughness was investigated, with results showing that PCL/CH (2 %) reduced surface roughness by 240 % compared to pure PCL film. Furthermore, the addition of CH imparted stable hydrophobic properties to the nanofiber film, with a water contact angle remaining steady at 107° after 20 s. L929 cell experiments confirmed that the nanofiber film exhibits good biocompatibility. Practical application studies using blueberries demonstrated that the PCL/CH (2 %) film effectively preserved freshness at room temperature for up to 5 days. These findings indicate that PCL/CH (2 %) films hold significant potential for use in fruit packaging applications.