Polyhydroxyalkanoate (PHA) is a biodegradable polymer and has wider applications in food packaging to medical. In extraction, the sustainability of solvents was focused on, where solvents either can be recycled completely or can be biodegraded. Based on that, such solvents were selected which are capable of recycling and can also perform multiple functions such as cell lyses, extraction, and separation from biomass. Three different solvents in extraction were utilized. Optimization of PHA extraction yield 96.32% was obtained at 120 °C incubation temperature, 30 min incubation time with cyclohexanone. The structural analysis of recovered PHA reveals that there is a methylene C-H stretching vibration of polymer chain, which is marked as indicator for Polyhydroxybutyrate-co-hydroxyvalvarate (PHBV). The melting temperature and degradation temperature of recovered PHBV was 164.45 °C and 285 °C, respectively, where degree of crystallinity was lower than standard PHBV, widens the application possibilities.