While we were compiling our manuscript, Liao and co-workers reported a photo-induced radical fluorosulfonamidation method for synthesizing sulfamoyl fluorides . In this work, we synthesize a series of highly reactive practical and air-stable radical fluorosulfonamidating reagents PNSF (2a-2c), which have been employed for the N-(fluorosulfonyl) sulfonamidation of various arenes and heteroarenes, sequential radical stereoselective fluorosulfonamidation, and the 1,2-difunctionalization of diverse alkenes to fabricate a range of functionalized sulfamoyl fluoride compounds.