An effective and reliable method for Pd-catalyzed highly regio- and stereocontrolled direct alkenylation of electron-deficient polyfluoroarenes with alkenyl iodides has been developed. The advantages of this reaction are its high regio- and stereoselectivity, mild reaction temperature (70 degrees C), and the use of readily available Pd(PPh3)(4). This approach provides a useful access to polyfluoroarylated derivatives of interest in both life and materials science.