Abstract: | A copper catalytic system was established for the stereoselective hydrodefluorination of gem‐difluoroalkenes through C−F activation to synthesize various Z fluoroalkenes. H2O is used as the hydrogen source for the fluorine acceptor moiety. This mild catalytic system shows good‐functional group compatibility, accepting a range of carbonyls as precursors to the gem‐difluoroalkenes, including aliphatic, aromatic, and α,β‐unsaturated aldehydes and even ketones. It serves as a powerful synthetic method for the late‐stage modification of complex compounds. |