The production and degradation of polyesters are two crucial processes in polyester materials’life cycle. In this work, multi-functional organocatalysts based on fluorides for both processes are described. Organofluorides were developed as catalysts for ring-opening polymerization of lactide (lactone). Compared with a series of organohalides, organofluoride performed the best catalytic reactivity because of the hydrogen bond interaction between F– and alcohol initiator. The Mn values of polyester products could be up to 72 kg mol–1. With organofluoride catalysts, the ring-opening copolymerization between various anhydrides and epoxides could be established. Furthermore, terpolymerization of anhydride, epoxide, and lactide could be constructed by the self-switchable organofluoride catalyst to yield a block polymer with a strictly controlled polymerization sequence. Organofluorides were also efficient catalysts for upcycling polyester plastic wastes via alcoholysis. Mixed polyester materials could also be hierarchically recycled.