Currently, the chemistry of organofluorine compounds is a leading and rapidly developing area of organic chemistry. The presence of fluorine largely determines specific chemical and biological properties of the molecule. This thematic issue covers the trends of organofluorine chemistry that have been actively developed in the last 1520 years in Russia. The review describes nucleophilic substitution and heterocyclization reactions involving fluorinated arenes and quinones and skeletal cationoid rearrangements in the polyfluoroarene series. The transformations involving CF3-substituted carbocations and radical cations are considered. Heterocyclization and oxidative addition reactions of trifluoroacetamide derivatives and transformations of the organic moiety in polyfluorinated organoboranes and borates with retention of the carbonboron bond are discussed. Particular attention is devoted to catalytic olefination using freons as an efficient synthetic route to fluorinated compounds. The application of unsymmetric