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Perfluoropyridine (PFPy) is an organofluorine compound that has been employed for a variety of applications, from straightforward chemical synthesis to more advanced functions, such as fluorinated networks and polymers. This can be directly attributed to the highly reactive nature of PFPy, especially towards nucleophilic aromatic substitution (SNAr). The aim of this review is to highlight the discovery and synthesis of PFPy, discuss its reactive nature towards SNAr, and to summarize known reports of the utilization and thermal analysis of PFPy containing fluoropolymers and fluorinated network materials.