(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) obtained from waste/wastewater using a mixed microbial culture (MMC) usually varies in its properties due to daily variation in the waste/wastewater composition applied as feedstock. In the current study, the average molecular weight (MW) of PHBV was purposely reduced from about 1 MDa to about 200 kDa by drying the PHBV-rich biomass at elevated temperature of 120 °C for 18 h to ease extraction and handling. Furthermore, conversion into value-added chemicals such as trans-crotonic acid (trans-CA) and trans-2-pentenoic acid (2-PA) by thermal decomposition (pyrolysis) benefits from the lower MW. For the extraction of low MW PHBV, the use of the bio-based solvents 2-methyltetrahydroxyfuran (2-MTHF) and dihydrolevoglucosenone (cyrene) was studied. The maximum extraction yield of 62 ± 3 % with purity of > 99 % was achieved with 2-MTHF at 80 °C for an hour with high biomass to solvent ratio of 5 % (g/mL). Cyrene-based extractions resulted in the highest yield of 57 ± 2 % with purity of > 99 % at 120 °C in 2 h with 5 % (g/mL) biomass to solvent ratio. The mass balance closure over the extraction process indicated that about 15 % and 10 % of polymer has remained in the residual biomass after extraction by 2-MTHF and cyrene, respectively. The performance of these new solvents to extract polymers with various average MW was compared to the benchmark extractions using chloroform and dimethyl carbonate (DMC). It was found that for the polymers with low average MW the extraction efficiency of the proposed solvents exceeds the benchmark solvents.