Potatoes are a source of starch, which is an eco-friendly alternative to petrochemicals in plastic production. Increasing potato production also creates agricultural waste that could be converted to potato peel starch (PPS) and developed as films. A response surface method approach was employed to optimize the bioconversion of PPS (2, 4, and 6% w/v) and compared with carboxymethyl cellulose (CMC)-based films. The microstructure analysis of PPSF showed increased thickness, decreased swelling power, water solubility, and vapor permeability, which were linked to increased molecular interactions as a function of PPS increments. However, low-starch PPSF exhibited high transparency, good mechanical properties, and thermal stability (high melting temperature), pliability, and accelerated seawater and soil biodegradation (~90%: 20 and 50 days, respectively). All films exhibited thermal stability at >100 °C and retained similar amorphous characteristics, evidenced by their flexibility, which confirmed the potential use for PPS in packaging perishable and cooled foods.