Poly(β‐hydroxyalkanoate)s (PHAs) are a class of aliphatic polyesters that can be efficiently synthesized by ring‐opening polymerization (ROP) of β‐lactones. The case of chiral racemic β‐substituted β‐lactones is particularly appealing since these monomers open the way to original tacticities and materials different from those biotechnologically produced. In this overview, after briefly surveying general considerations associated to the ROP of β‐lactones and metal‐based catalysts used in stereoselective ROP of racemic β‐butyrolactone, special emphasis is given to discrete rare earth catalysts that have allowed the preparation of highly syndiotactic poly(3‐hydroxybutyrate)s. Recent developments – such as preparation of stereocontrolled PHAs with pendant structural groups via (co)polymerization of functional β‐substituted β‐lactones, and highly alternating copolymers obtained by ROP of mixtures of enantiomerically pure but different monomers – are also discussed.
