Polybenzoxazines belong to next-generation highly crosslinked thermostable resins with physical properties that go far beyond traditional high temperature polymer networks. Due to a unique set of properties, they have significant advantages over other existing thermosets. Commercial availability and wide structural diversity of the starting feedstock for the polybenzoxazines synthesis also are important benefits of such polymer systems that allow reducing production cost with simultaneous broadening of their useful properties. In our review, we discuss recent advancements in the field of fluorinated polybenzoxazines and their applications in the area of fuel cells, electronics, superhydrophobic and superoleophilic membranes for water purification, and some others. The review begins with consideration of general strategies for the synthesis of fluorinated polybenzoxazines. Next, we critically analyze various approaches to design of fluorinated benzoxazine-containing monomers and prepolymers, as well as the ways for incorporating fluorine atoms into their chemical structure. We highlight different pathways for fabrication of fluorinated polybenzoxazines and their composites with the emphasis on the structure-properties relationships in this remarkable polymer class. Finally, the review provides a summary of the most recent applications of polybenzoxazines and envisages future directions of research in the area of chemistry of fluorinated benzoxazines.