Food waste is a major sustainability challenge, particularly for highly perishable vegetables such as broccoli, where quality deterioration contributes significantly to losses throughout the supply chain. This study evaluated the effectiveness of different packaging materials and microperforation strategies for preserving the quality of fresh-cut broccoli during refrigerated storage. Broccoli florets were packaged in conventional petroleum-based plastics and in biodegradable polylactic acid (PLA), each tested with and without microperforations, and stored at 3 °C for 20 days. Internal gas composition, fermentation risk, weight loss, odour, and overall appearance were monitored throughout storage. Non-microperforated OPP and PLA generated highly restrictive atmospheres characterized by very low O₂ and elevated CO₂ concentrations, increasing fermentation risk and accelerating sensory deterioration. In contrast, microperforated treatments maintained more favourable gas compositions, reduced fermentation risk, and better preserved odour and visual quality, although they resulted in greater weight loss. Principal component analysis confirmed that microperforation was the main factor influencing package atmosphere and quality preservation, exceeding the effect of polymer type. Among the tested systems, microperforated PLA provided the best balance between respiratory conditions and sensory quality. These findings demonstrate that microperforated biodegradable PLA packaging represents a promising strategy to maintain fresh-cut broccoli quality while supporting more sustainable packaging solutions and contributing to food waste reduction.