Аннотация:1,1,1,3,3,3-Hexafluoroisopropanol (HFIP) is a solvent with properties in the extreme. Being used in specific scopes for more than half a century, nowadays, it has become a hot topic in complex organic transformations. The application of HFIP is gaining wide perspectives not only in synthetic chemistry but in biology and chemical physics. This article discloses the unusual nature of HFIP and its extraordinary solvation effects upon different classes of molecules and on C—H functionalization reactions in general. The structure and coordinating modes of the solvent make it possible to infer the impact of HFIP on the reagents activation, intermediates stabilization, and products outcome in C—H functionalization reactions.