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The chemical recycling of a small array of fluoropolymers including poly(vinylidene difluoride) is reported. Using a catalytic combination of BF3•OEt2 and BF3•PCy3, equivalents of HF can be harvested from these fluoropolymers and delivered to acid anhydrides to generate the corresponding acyl fluorides. Catalytic conditions were established and optimised using fluoroethane (HFC-161) as a model substrate and can be applied to a range of acid anhydrides, including acetic anhydride. Mechanistic studies suggest that two competitive processes involving both hydrofluorination and fluoroalkylation of the acid anhydride are in operation. Spectroscopic studies in combination with DFT calculations shed light on the roles that BF3•OEt2 and BF3•PCy3 play in these processes. The methodology was applied to a series of pristine fluoropolymers (PVDF, PVF, ETFE, HFP-PVDF) along with post-consumer materials including PVDF recovered from a Li-ion battery. Quantitative analysis suggests that on average one fluorine atom per the repeat unit of PVDF had been transferred to the acyl fluoride. Spectroscopic analysis (powder XRD, XPS, IR spectroscopy, DSC, TGA) of the recovered fluoropolymer showed that the reaction occurs with decrease in the crystallinity of PVDF, with loss of the a-phase of pristine material. Defluorination introduces new unsaturated C=C and oxygen-containing functional groups into the fluoropolymer and drastically lowers the onset temperature for its thermal decomposition. This approach not only has the potential to recycle fluorine content of selected fluoropolymers but create new fluorinated materials with different properties to pristine polymers.