As　a　distinctive　functional　group　with　remarkable　reactivity　in　organic　synthesis,　sulfonyl　fluoride　has　demonstrated　vast　application　potential　in　numerous　fields,　including　drug　synthesis,　chemical　biology　and　materials　science.　Nonetheless,　owing　to　the　growing　demand　for　environmental　sustainability　in　modern　chemical　synthesis,　traditional　methods　of　sulfonyl　fluoride　synthesis　are　under　reconsideration.　Conversely,　free　radical　fluorosulfonylation　has　emerged　as　a　vital　method　of　introducing　the　sulfonyl　fluoride　group,　attributed　to　its　superior　efficiency,　minimal　energy　consumption,　and　eco-friendliness.　This　article　will　concentrate　on　the　recent　advancements　in　the　reaction　of　free　radical　fluorosulfonylation.　©　2025　Shanghai　Institute　of　Organic　Chemistry,　Chinese　Academy　of　Sciences.