The fluoride anion-initiated reaction of phenyl aromatic carboxylates with (trifluoromethyl)trimethylsilane (Me₃SiCF₃) that results in the formation of O-silyl-protected 2-aryl-1,1,1,3,3,3-hexafluoroisopropanols is reported. A phenoxide anion, generated during the trifluoromethylation of the phenyl carboxylate, also activates the Me₃SiCF₃, which permits a catalytic amount of the fluoride anion source to be used. Various functional groups, which can be used for further elaboration, are tolerated in the reaction.