Polyhydroxyalkanoates (PHAs) represent a group of biopolymers that are synthesized by many bacteria as storage compounds and deposited as insoluble cytoplasmic inclusions. Because they have many putative technical and medical applications, PHAs may play an important role in human life in the future. Therefore, for academic interest the bacterial PHA metabolism has been studied in much detail. In the past decade much new and unexpected information about the metabolism of PHA in bacteria became available. Aspects of the biogenesis of PHA granules in bacteria become more and more important in the literature. Several enzymes, proteins, and mechanisms of regulation are involved in PHA biosynthesis and PHA granule biogenesis. The intention of this review is to give an overview about our current knowledge of the structure of the PHA granule surface and the PHA granule-associated proteins involved in biogenesis and degradation. The focus is on the PHA synthases, the intracellular PHA depolymerases, the phasins, and the transcriptional regulator PhaR, which are the main actors in biosynthesis and intracellular degradation of PHAs and formation of PHA granules. In addition, putative applications of PHA granules and PHA granule-associated proteins in nanotechnology are discussed.