A new strategy for the construction of a C=C-CF3 subunit has been developed via CuBr-catalyzed domino cyclization-trifluoromethylation of homopropargyl amines with Umemoto's reagent. 4-Trifluoromethyl-2,3-dihydro-pyrroliums were produced in high yields. The usefulness of these products has been demonstrated by the transformation of them into various other trifluoromethylated molecules.