We report herein the three-component radical addition reaction of SF 5 Cl, alkene and diazo compounds for the selective formation of α-alkyl-α-SF 5 carbonyl compounds. The three-component addition reaction proceeded through the first reaction of SF 5 radical with the diazo compound followed by the addition of the in situ generated carbon radical to alkene. The synthetic useful α-allyl-α-SF 5 carbonyl compounds were successfully prepared when allyl trimethylsilanes were used as the alkene substrates. Furthermore, the three-component adducts formed from SF 5 Cl, α-diazoacetophenones and vinyl acetates were converted into pentafluorosulfanylfurans. This transformation provided a practical and efficeint method for the synthesis of pentafluorosulfanylfurans.