Synthesis of sulfamoyl [F-18]fluorides has been a challenging topic owing to the inefficient nucleophilic radiofluorination of sulfamoyl derivatives. Herein, we report an F-18/F-19 isotopic exchange approach to synthesize various sulfamoyl [F-18]fluorides, otherwise inaccessible via direct synthesis from amines, with high radiochemical yields up to 97% (30 examples). This late-stage labeling protocol offers an efficient route to yield functionalized molecules by diversifying the chemical library possessing sulfamoyl functionalities through nucleophilic F-18 incorporation within nitrogen-containing sulfur(VI) frameworks.