Background Polyhydroxyalkanoates (PHAs) synthesized by bacteria are the primary source for production of biodegradable bioplastics. PHAs can be produced by microbial cultures fed with renewable feed stocks. PHAs are a great opportunity for the polymer industry. While some bacterial species produce mainly PHB homopolymers consisting only of 3HB monomers, other species can synthesize various PHAs, depending on availability of intermediate precursors. The enzymes synthesizing the polymers, PHA syntheses are encoded by the PhaC genes. Differences in primary and secondary structure determine the capacity to accommodate various hydroxyalkanoate substrates and to form shortchain-length or medium-chain-length PHAs. In this review we discuss the enzyme structure and differences at the base of the characteristic polymers formed. Finally, we review innovative methods applied to biofermentor and on-line fermentation to monitor the production of PHAs, finalized to optimization of fermentation conditions, and the extraction methods available.