A general and facile synthetic method for β-fluoroenones from silyl enol ethers or ketones, with a copper-amine catalyst system, has been developed. The reaction proceeded by a tandem process of difluoroalkylation-hydrolysis-dehydrofluorination. This method is characterized by high yields, excellent Z/E ratios, a low-cost catalyst, and a broad substrate scope. The synthetic potential of β-fluoroenones has been demonstrated by the construction of various complicated organofluorine molecules.