Fluorinated polystyrene has a number of attractive properties, but its synthesis is rather complicated. In this regard, it seems attractive to obtain polyfluorstyrene by direct fluorination of polystyrene under “mild” conditions – in the form of a suspension in a perfluorinated liquid. The fluorinated polymer was characterized by IR and ¹⁹F and ¹³C solid-state NMR spectroscopy. It was shown that non-destructive hydrogen-substituting fluorination prevails under these “mild” conditions; fluorination occurs into the benzene ring and into the main carbon chain.