Abstract Regularities were revealed of polyfluoroalkyl chlorosulfites synthesis by reaction of thionyl chloride with associates polyflorinated alcohol-triethylamine and of a new reaction with polyfluorinated alcohols (catalysis by amides), resulting in symmetrical simple polyfluoroalkyl ethers. New polyfluoroalkylation reactions of aliphatic (including polyfluorinated) alicyclic, benzyl alcohols, phenol, carboxylic acids and their salts with ...