An unprecedented three-component copper-mediated vicinal trifluoromethylation-allylation of arynes is described. A wide range of structurally diverse trifluoromethylated allylarenes can be quickly assembled in one step. The application of the method has been demonstrated in the expedient synthesis of the CF3-containing analogue of the antispasmodic drug papaverine. The new reactivity of the [CuCF3] reagent, which is generated from the inexpensive industrial byproduct fluoroform, is revealed with unique advantages.