Palladium-catalyzed cross-coupling reaction of 4-trifloxy-quinolin-2(1H)-ones or 4-chlorocoumarins with polyfluoroarenes has been successfully developed. Under mild conditions, the reactions afforded 4-polyfluoroarylquinolin-2(1H)-ones and 4-polyfluoroarylcoumarins, which feature a wide range of bioactive compounds, with good yields.