Antimicrobial food packaging materials are in high demand. This study develops H2O2-releasing composite films by incorporating CaO2 into poly(lactic acid)/polyethylene glycol (PLA/PEG) composites through melt extrusion. The structural, thermal, mechanical, and antimicrobial properties of the PLA/PEG/CaO2 composite films were characterized. PEG, which acts as a plasticizer and hydrophilic agent, enhances film flexibility and moisture uptake, facilitating CaO2 hydrolysis and H2O2 release. Composite films containing ≥ 20 wt% PEG released 67 ppm of H2O2 within 12 h and achieved 99.999% bacterial reduction against Escherichia coli and Staphylococcus aureus. Storage tests with cherry tomatoes demonstrated that PLA/PEG/CaO₂ films delayed ruit deterioration and extended shelf life to 13 d. Migration testing using standard food simulants confirmed that films with ≤ 20 wt% PEG comply with the European Union regulatory limit (10 mg/dm2). The developed PLA/PEG/CaO2 composite films are thus safe, and effective antimicrobial packaging materials, especially for fresh produce.