Phenyl(trifluoromethanesulfonate)(3,3,3-trifluoropropynyl)-lambda(3)-iod ane was prepared from tributyl(3,3,3-trifluoropropynyl)stannaneand PhI(CN)OTf. The molecular structure was disclosed by X-ray diffraction analysis to form T-shape geornetry with the hypervalent iodine atom as the central point. The iodonium salt underwent smoothly the Diels-Alder reaction with 1,3-dienes, furans, and pyrrole to give trifluoromethyl-substituted cyclohexadienes in good to high yields, respectively, in contrast to the corresponding nonfluorinated counterpart.