An ew decarboxylative perfluoroalkylation of vinyl bromides has been developed. The use of copper(I) trifluoroacetate complex (phen)Cu(O 2 CCF 3 )( 1)a nd perfluorocarboxylate complexes [(phen) 2 Cu](O 2 CR F )( 2;R F = C 2 F 5 , n-C 3 F 7 , n-C 4 F 9 , n-C 5 F 11 )a sr eagents allowsf or the efficient synthesis of trifluoromethylated and perfluoroalkylated olefins, respectively.V inyl bromides comprising ar ange of functionalities (e.g.,m ethoxy,e ster,n itrile,n itro, trifluoromethyl, chloride, and benzo[d][1,3]dioxole) were successfully accommodated. The decarboxylative trifluoromethylation and perfluoroalkylation reactions also proceeded with retention of the double-bond stereochemistry of alkenes after the reaction was completed.Scheme1.Methods for the preparation of perfluoroalkylated alkenes.[a] C.