Abstract.Polyhydroxyalkanoates are a family of natural polyesters being produced as intracellular carbon and energy reserves by a wide variety of microorganisms. They have developed rapidly in both research and development efforts globally in the last 15 years. Till now, over 100 different types of PHAs have been successfully biosynthesized using both genetic engineering and fermentation techniques. Their unique biodegradable, biocompatible and thermoplastic characteristics make PHAs promising candidates for the commodity and biomedical applications. This review focused on the chemical synthesis of the derivatives of the biosynthesized PHAs.