With the development of SuFEx chemistry, how to introduce fluorosulfonamide groups into complex biologically relevant scaffolds and drug molecules efficiently is attractive. Along this line, this radical fluorosulfonamidation protocol was applied to the late-stage modification of bioactive molecules (Figure ). Various natural products and pharmaceutical derivatives, including melatonine, fludioxonil, N-Tosyl-L-alanine 3-indoxyl ester, angelicin, psoralen, theophylline, cosaldon, tangeretin were well-tolerated, furnishing the corresponding late-stage modified products (5ai-5ak, 5am-5aq) in moderate to good yields. In addition, the derivatives of 3-indolepropionic acid, tryptophan and ribonic also effectively participated in this transformation, afforded the desired products (5al, 5ar-5at) in moderate to good yields.