USABLE Packaging project has developed an innovative value chain based on mixed microbial cultures using organic wastes as feedstock to produce prototypes of PHA-based items that were compared to their commercial counterparts, so the expected better environmental performance can be checked. To do so, a cradle-to-grave life cycle assessment was carried out. The system was modeled integrating all available knowledge, from pilot-scale data to process simulators, and following upscaling frameworks. PHA-based items outperform their commercial counterparts since they show environmental benefits thanks to the avoided electricity obtained in the cogeneration heat and power unit within the PHA production; however, these environmental benefits are very sensitive to the substituted electricity environmental burdens. The different levels of development and market implementation are seen as critical and therefore attention should be paid on how upscaling affects the results and interpretation of the LCA while serving as a guide for process and product development.