In recent years, the development of environmentally friendly packaging materials using biodegradable polymers has emerged as a key challenge for scientists and consumers in response to resource depletion and environmental issues caused by plastic packaging materials. Starch and polyvinyl alcohol (PVA) are being recognized as excellent candidates for producing biodegradable food packaging films. Polymer blending has emerged as a practical approach to overcome the limitations of biopolymer films by developing films with unique properties and enhancing overall performance. This review briefly introduces the molecular structure and properties of starch and PVA, summarizes the common preparation methods and properties of starch/PVA blend films, and focuses on different strategies used to enhance starch/PVA blend films, including nanoparticles, plant extracts, and cross-linking agents. Additionally, this study summarizes the application of starch/PVA blend films as active and smart packaging in food preservation systems. This study demonstrates that starch and PVA blends have potential in manufacturing biodegradable food films with excellent properties due to their excellent compatibility and intermolecular interactions, and can be used as packaging films for a variety of foods to extend their shelf life.