The biotechnological production of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) derived from organic waste streams by mixed microbial communities is well established at the pilot-level. However, there is limited research on the recovery of the biopolymer from the microbial biomass, while its impact on product quality and product costs is major. When applying solvent extraction, the choice of solvent has a profound influence on many aspects of the process design. This study provides a framework to perform a systematic solvent screening for PHBV extraction. First, a database was constructed of 35 solvents that were assessed according to six different selection criteria. Then, six solvents were chosen for further experimental analysis, including 1-butanol, 2-butanol, 2-ethyl hexanol (2-EH), dimethyl carbonate (DMC), methyl isobutyl ketone (MIBK), and acetone. The main findings are that the extractions with acetone and DMC obtained the highest yields (91-95%) with reasonably high purities (93-96%), where acetone had a key advantage of the possibility to use water as anti-solvent. Moreover, the results provided new insights in the mechanisms behind PHBV extraction by pointing out that at elevated temperatures the extraction efficiency is less determined by the solvent's solubility parameters and more determined by the solvent size. Although case-specific factors play a role in the final solvent choice, we believe that this study provides a general strategy for the solvent selection process.