A mild and efficient palladium-catalyzed cross-coupling between fluorinated vinyl chloride and arylboronic acids is described. The use of ligand B successfully overcomes the strong electronic withdrawing of trifluoromethylated substrates and allows the efficient synthesis of a wide range of α and α,β-trifluoromethyl containing olefins. By using this method, the key intermediate for synthesis of Efavirenz can be obtained in a simple route. The efficient conversion of two freon molecules into useful α and α,β-trifluoromethyl containing olefins is a useful route in organic chemistry.