The use of plastic in the food industry has led to adverse environmental impacts due to the generation of solid waste. Therefore, the food packaging industry must adopt eco-friendly alternatives. In this study, starch was extracted from green banana peels using two different methods: using only the aerenchyma and using the whole peel. Nine formulations (F1-F9) of biodegradable starch/glycerol films were prepared and analyzed. FT-IR spectroscopy identified the presence of characteristic functional groups. XRD analysis revealed that the films' crystallinity increased for F7, F8, and F9, which utilized the entire peel, as opposed to the others that used only the aerenchyma. Scanning electron microscopy (SEM) illustrated that the films exhibited similar morphologies, roughness, heterogeneity, and variability attributed to the films' preparation technique. The films' thermal degradation was evaluated using TGA, showing approximately 80% total mass weight loss at around 700 °C, with the highest loss occurring around 290 °C. The degradation peak in the thermogravimetric derivative was primarily attributed to the depolymerization of organic components. Finally, the films' mechanical, solubility, and vapor permeability properties were optimized to identify the most suitable formulation for food packaging. F3 was determined to be the most appropriate formulation due to its highest mechanical properties and lower vapor permeability and solubility compared to a commercial polyethylene film.