Radical　fluorosulfonylation　is　emerging　as　an　appealing　approach　for　the　synthesis　of　sulfonyl　fluorides,　which　have　widespread　applications　in　many　fields,　in　particular　in　the　context　of　chemical　biology　and　drug　development.　Here,　we　report　the　first　investigation　of　FSO2　radical　generation　under　electrochemical　conditions,　and　the　establishment　of　a　new　and　facile　approach　for　the　synthesis　of　β-keto　sulfonyl　fluorides　via　oxo-fluorosulfonylation　of　alkynes　with　sulfuryl　chlorofluoride　as　the　radical　precursor　and　air　as　the　oxidant.　This　electrochemical　protocol　is　amenable　to　access　two　different　products　(β-keto　sulfonyl　fluorides　or　α-chloro-β-keto　sulfonyl　fluorides)　with　the　same　reactants.　The　β-keto　sulfonyl　fluoride　products　can　be　utilized　as　useful　building　blocks　in　the　synthesis　of　various　derivatives　and　heterocycles,　including　the　first　synthesis　of　an　oxathiazole　dioxide　compound.　Furthermore,　some　β-keto　sulfonyl　fluorides　and　derivatives　exhibited　notably　potent　activities　against　Bursaphelenchus　xylophilus　and　Colletotrichum　gloeosporioides.　©　2021　Wiley-VCH　GmbH.