The fluorine-containing organic compounds are becoming privileged in pharmaceuticals,agrochemicals and functional materials.[1]Described herein is a mild and efficient method for the radical addition of olefins with TMS-CF3 and TMS-CF2R to deliver various α-fluorinated ketones and α-fuoroolefinated ketone analogues.α-CF3-substituted carbonyl compounds as versatile building blocks have been widely used in synthesis of a variety of fluorinated compounds.[2]We treated styrene with TMS-CF3 in the presence of AgF in DMF at room temperature in an oxygen atmosphere,and the corresponding products were obtained in 60-90% yields (Scheme 1).This transformation was also expanded to other fluorinated substrates,such as TMS-CF2COOEt and TMS-CF2CF3.The undesired fluoroolefinated products were delivered in moderate to high yields (Scheme 2).The fluoroalkene group is considered isopolar and isosteric with amide and possesses distinct biophysical properties,including decreasing H-bond donating and accepting abilities.