A novel palladium-catalyzed intermolecular aminofluorination of styrenes, with N-fluorobenzenesulfonimide (NFSI) functioning not only as a fluorinating reagent but also as an aminating reagent, has been developed. The reaction afforded vicinal fluoroamine products With very high regioselectivity. This transformation may involve fluoropalladation of styrene as a key step for C-F bond formation, The bidental nitrogen ligand is crucial to achieving the transformation successfully.