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Biodegradable and biocompatible polymers, polyhydroxyalkanoates (PHAs), are widely used in medicine for production of a wide range of medical devices (screws and plates for bone fixation, bowel patches and plugs, cardiovascular stents, wound coverings, nerve guidance conduits, surgical meshes etc.) and dosage formulations for sustained and targeted drug delivery. PHAs can be used also in bioengineering, e.g. for tissue engineering, as scaffolds for cell factories, for developing experimental disease models in vitro, e.g. 3D tumor growth model. The medical and pharmaceutical industry applies mainly PHAs that obtained by chemical synthesis, but the interest in the medical use of natural PHAs obtained biotechnologically is also growing. Synthetic PHAs are biomimetic analogs of bacterial poly(3-hydroxybutyrate) (PHB) and other natural PHAs. We developed an effective precursor feeding technology of PHB and its copolymers production using bacterial strain-producers from genus Azotobacter, which allow to synthesize various PHAs with desired properties and studied physicochemical and biological properties of obtained biopolymers. The main biomedical properties of PHB and other natural PHAs: biodegradability, biocompatibility, and bioactivity are directly related to the various functions of these biopolymers in nature, e.g. their physiological role in the bacterial cell. The possibility of biosynthesis and biodegradation of PHB by different symbiotic and infectious human and animal bacteria, particularly, multiple bacteria of intestinal microbiota is therefore particularly interesting. There is still a lot of obscure in the problem of endogenous PHB in human and animal tissues: can the microbiota bacteria be a source of endogenous PHB? Thus, the biological functions of PHB and other natural PHAs in bacteria and eukaryotes, including human, are, apparently, the most important reason for using both natural and synthetic PHAs in medicine and pharmacy.