Polymer nanofibers exhibit unique nanoscale effects, high specific strength and modulus, exceptional design flexibility, large aspect ratios, and substantial specific surface areas. These characteristics have drawn significant attention in emerging fields such as flexible electronics, 5G communications, and new energy vehicles. Notably, poly(p‐phenylene benzobisoxazole) nanofibers (PNFs) present the best thermal stability and flame retardancy among all known polymer nanofibers. Furthermore, due to the highly oriented molecular chains and orderly structure, PNFs demonstrate superior thermal conductivity compared to conventional polymer nanofibers, thus garnering significant attention and favor from researchers. This paper summarizes the latest research progress of PNFs, detailing three preparation methods (electrospinning, mechanical dissociation, and protonation) along with their respective advantages and disadvantages. It also elucidates the current development status of PNFs in applications such as flame retardancy, thermal conduction, electrical insulation, electromagnetic shielding, and battery separators, and discusses the challenges and prospects faced by PNFs. This paper aims to provide theoretical guidance for the preparation and application of PNFs, enhancing their potential in advanced applications, and further expanding their application scope.