[Bis(trifluoroacetoxy)iodo]pentafluorobenzene (CAS# 14353-88-9) is a useful iodine(III)-containing building block used in the [2+2+1] cycloaddition of alkynes and nitriles in the preparation of imidazoles. Also a source of perfluoroalkyl radicals, [Bis(trifluoroacetoxy)iodo]pentafluorobenzene has been applied to the metal-free fluoroalkylation of organic molecules.