This work aimed to investigate various methods of polyhydroxyalkanoates (PHA) extraction and to optimize the recovery in the view of reducing solvents’ use and waste. The extraction tests were applied on PHA-rich biomass collected at the end of the accumulation step, conducted both at pilot and lab scale. PHA-rich biomass obtained from the lab scale process was produced from synthetic feedstock (mixture of acetic and propionic acids), while fermented organic waste was used for PHA production at pilot scale. In the extraction tests, different solutions of NaOH, also in combination with a surfactant (sodium dodecyl sulfate, SDS), were used to recover the polymer from the non-polymeric cellular material (NPCM). Different times (3, 6 and 24 h) and concentrations (0.05 – 1 M) were tested, evaluating also the effect of adding SDS (0.1 % w/v). As a benchmark, solvent extraction with chloroform and oxidation with NaClO were also conducted. Finally, extracted samples were characterized through several techniques: DSC, TGA, GC-FID, capillary viscosimetry. Alkaline treatment at short times and low concentrations resulted to be more efficient in terms of purity (85 – 99 % w/w PHA) and recovery (higher than 80 % w/w), than higher concentration. On the other hand, the presence of SDS had dramatic effects on the recovery (lower than 50 % w/w) and also on the molecular weight, which was two folds lower than that obtained from alkaline extraction. Overall, extraction with aqueous phase reagents had no effects on thermal properties, which resulted to be in the range of those reported in literature.