Polyvinyl alcohol (PVA)–bacterial succinoglycan (SG) biodegradable films were developed through a solvent-casting method. Effects of the PVA/SG ratio on the thickness, transmittance, water holding capacity, and structural and mechanical properties were investigated by various analytical methods. All the prepared films were transparent and uniform, and XRD and FTIR analyses confirmed that PVA was successfully incorporated into SG. The films also showed excellent UV-blocking ability: up to close to 80% with increasing SG concentration. The formation of effective intermolecular interactions between these polymers was evidenced by their high tensile strength and moisture transport capacity. By measuring the biodegradation rate, it was confirmed that films with high SG content showed the fastest biodegradation rate over 5 days. These results confirm that PVA/SG films are eco-friendly, with both excellent biodegradability and effective UV-blocking ability, suggesting the possibility of industrial applications as a packaging material in various fields in the future.