Processes for the extraction of PHAs from biomass, said processes comprising: combining the biomass containing the PHAs with a single main solvent to form a biomass liquor; heating the biomass liquor to at least partially solubilize the PHAs from the biomass to form a PHA liquor; separating the biomass from the PHA liquor to form a PHA-enriched liquor; evaporating from 0% to about 50% of the single main solvent from the PHA-enriched liquor to form a solvent vapor and a concentrated PHA-enriched liquor; and cooling the concentrated PHA-enriched liquor to form precipitated PHAs and an impure solvent liquor. Optionally, further recovering the precipitated PHAs from the impure solvent liquor by filtration under pressure. A PHA-enriched liquor and a concentrated PHA-enriched liquor.