A nickel-catalyzed three-component coupling reaction of tetrafluoroethylene (TFE) and N-sulfonyl-substituted imines with silanes that furnishes a variety of fluorine-containing amines is disclosed. Stoichiometric experiments revealed that the aza-nickelacycles generated upon oxidative cyclization of TFE and N-sulfonyl-substituted imines on Ni(0) were identified as the key intermediates in this catalytic reaction. A single-crystal X-ray diffraction analysis of such an aza-nickelacycle revealed that the O atom of the N-sulfonyl group stabilizes the key intermediate via coordination to the nickel center.