Polyhydroxyalkanoic acids (PHA) represent a complex class of storage polyesters that are synthesized by a wide range of different Gram-positive and Gram-negative bacteria as well as by some Archaea and that are deposited as insoluble cytoplasmic inclusions. PHA synthases, which are the key enzymes for PHA biosynthesis, have been characterized in much detail. At present 42 PHA synthase structural genes from 38 different bacteria have been cloned, and from 30 genes the nucleotide sequences were obtained. The strategies successfully employed to clone these genes and the current knowledge on the organization of the PHA synthase genes and other genes encoding proteins related to PHA metabolism will be compiled. In addition, the primary structures of the 30 PHA synthases were aligned and analyzed with respect to highly conserved amino acids and biochemical features. The direction, in which research should proceed, in order to increase our knowledge on biosynthesis of PHAs and to utilize this knowledge for the development of technically and economically feasible processes for the production of these polyesters will be outlined.