Zn­(HMDS)2 as a simple, biocompatible, efficient, and supporting ligand-free metal catalyst has been achieved for polyesters synthesis and degradation. The catalyst not only has a powerful capacity for ring-opening polymerization of various lactones to obtain diverse sustainable polyesters, such as poly­(lactide), poly­(3-hydroxybutyrate), and poly­(caprolactone), etc., with controlled molecular weights and narrow molecular weight distributions, but also can be used to degrade polyesters into valuable depolymerization products with excellent yields and chemoselectivity, demonstrating a truly circular materials economy approach to sustainability.

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