We report herein the three‐component radical addition reaction of SF5Cl, alkene and diazo compounds for the selective formation of α‐alkyl‐α‐SF5 carbonyl compounds. The three‐component addition reaction proceeded through the first reaction of SF5 radical with the diazo compound followed by the addition of the in situ generated carbon radical to alkene. The synthetic useful α‐allyl‐α‐SF5 carbonyl compounds were successfully prepared when allyl trimethylsilanes were used as the alkene substrates. Furthermore, the three‐component adducts formed from SF5Cl, α‐diazoacetophenones and vinyl acetates were converted into pentafluorosulfanylfurans. This transformation provided a practical and efficeint method for the synthesis of pentafluorosulfanylfurans. A three‐component radical reaction of SF5Cl, alkenes, and diazo compounds for synthesis of α‐alkyl‐α‐SF5 carbonyl compounds was developed. Furthermore, the three‐component adducts formed from SF5Cl, α‐diazoacetophenones and vinyl acetates were converted into pentafluorosulfanylfurans.