Organocatalysis offers a number of prospects in the polymer community and presents advantages over metal based and bio-organic methods. The use of organic molecules for performing chemical reactions is not a new concept, and any research into organocatalytic reactions builds on a respected history. Compared to the organocatalysis of large lactones, which began in the early 2000s, the examples presented here will demonstrate that few metal-free initiating systems had been applied to beta-lactones well before the beginning of the current millennium. These metal-free initiating systems present indisputable advantages over metal-based processes. In the following paper, ring-opening polymerizations (ROPs) of various beta-lactones for the preparation of poly(hydroxyalkanoate)s will be presented, as will the types of mechanisms involved, that is, zwitterionic and anionic, and cationic or supramolecular-based ROPs. The advantages and drawbacks of the different technics will be discussed in the domain, which, for us, is important in the overall production of bioplastics. (c) 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 657-672