Bioplastics are frequently utilized in daily life, particularly for food packaging and carrier bags. They can be delivered to biogas plants through a separate collection of the organic fraction of municipal waste (OFMSW). The increased demand for and use of bioplastics aimed at mitigating plastic pollution raises significant questions concerning their life cycle and compatibility with waste management units. Anaerobic digestion (AD) in OFMSW is a valuable resource for biogas production. In this work, the valorization of poly-L-lactic acid (PLLA) composed of food waste within the Biowaste to Bioplastic (B2B) Project framework was studied in laboratory and pilot-scale anaerobic liquid conditions. Taking into account that the addition of PLLA to biowaste can increase biogas production, we performed laboratory-scale anaerobic tests on food waste enriched with different molecular-weight PLLAs produced from food waste or commercial PLLA at a mesophilic temperature of 37 °C. PLLA with the highest molecular weight was subjected to AD on the pilot scale to further validate our findings. The addition of PLLA increased biogas production and had no apparent negative impact on the operation of the reactors used in the laboratory or on the pilot scale. Biogas production was higher when using PLLA with the lowest molecular weight. In the pilot-scale experiments, co-digestion of FW with PLLA increased biogas production by 1.1 times. When PLLA was added to the feed, biomethane was 8% higher, while volatile solids (VS) and total chemical oxygen demand (TCOD) removal were almost the same. Importantly, no effect was observed in the operation of the digesters.