Using antifungal food packaging films presents a significant opportunity to prolong the shelf-life of food products. In this work, a chitosan-polyvinyl alcohol antibacterial film, enriched with clove essential oil (CS/PVA/CEO), was developed for preservation effects on yellow peaches, and its physical properties and structure were investigated. The good compatibility and thermal stability of CS/PVA/CEO film were demonstrated via scanning electron microscopy, Fourier-transform infrared spectroscopy, and thermogravimetric analysis. Mechanical properties are exhibited at a 0.75% CEO concentration: the tensile strength is (25.09 ± 0.32) MPa, elongation at break is (291.23 ± 2.53)%, water vapor permeability is (0.479 ± 0.005) g·mm·m−2·h−1·kPa−1, water resistance is (18.57 ± 0.35)%, and water resistance is (9.70 ± 0.26)%. During the 11 days of storage at temperatures ranging from 23 °C to 26 °C and 26 days of storage at 4 °C–5 °C, the CS/PVA/CEO film exhibited effective preservation of yellow peach fruits. CS/PVA/CEO group extended 3–4 d at room temperature and 5–10 d at 4 °C of yellow peaches preservation compared with the CS/PVA and control groups. This effectiveness was evaluated based on various parameters, including fruit appearance, decay rate, respiratory intensity, malondialdehyde concentration, firmness, total soluble solids, and titratable acidity. Therefore, adding CEO into the antifungal film demonstrated excellent potential in enhancing the preservation of yellow peaches.