Abstract We report herein a general one‐pot perfluoroalkylation/dehydrohalogenation protocol for the selective perfluoroalkenylation of silyl dienol ethers in their γ position. Importantly, this methodology is applicable to the synthesis of a wide range of γ‐perfluoroalkenylated enals, enones and α,β‐unsaturated amides. Various perfluoroalkenyl moieties could be efficiently introduced, with an important impact on the E / Z diatereoselectivity of the newly formed fluorinated double bond.