The escalating environmental impact of plastic packaging waste necessitates sustainable alternatives in food packaging. This study explores starch-based films derived from cassava and potato as viable substitutes, aiming to mitigate plastic pollution and enhance environmental sustainability. Utilizing a casting method, formulations optimized by CCRD were characterized for their physical, physicochemical, and morphological properties. Comprehensive analysis revealed both cassava and potato starch films to exhibit robust structural integrity, high tensile strength (up to 32.6 MPa for cassava starch films), and semi-crystalline morphology. These films demonstrated low water vapor permeability and moderate solubility, akin to conventional low-density polyethylene used in packaging. Differential scanning calorimetry indicated glass transition temperatures between 116.36 °C and 119.35 °C, affirming thermal stability suitable for packaging applications. Scanning electron microscopy confirmed homogeneous film surfaces, with cassava starch films (C4-15) exhibiting superior transparency and uniformity. X-ray diffraction corroborated the films’ semi-crystalline nature, unaffected by sorbitol content variations. Despite their mechanical and thermal suitability, further enhancements in thermal degradation resistance are essential for broader thermoprocessing applicability. These findings underscore the potential of starch-based films to be used as lids or other part of a food package, decreasing the plastic dependency in food packaging, contributing decisively to waste reduction and environmental preservation.