A　novel　and　efficient　approach　for　the　synthesis　of　α,　β-unsaturated　sulfones　through　heterogeneous　photocatalyzed　C−S　coupling　reactions　have　been　developed.　The　use　of　molten-salt　method　derived　carbon　nitride　(MCN),　a　transition　metal-free　polymeric　photocatalyst,　combined　with　enhanced　crystallinity　and　potassium　iodide　as　an　additive,　effectively　modulates　photogenerated　reactive　redox　species,　markedly　increasing　the　overall　reaction　selectivity.　This　method　achieves　the　shortest　reaction　time　(2　h)　with　high　yield　(up　to　95　%)　among　the　reported　heterogeneous　catalytic　C−S　bond　formation　reactions,　matching　the　efficiency　of　the　homogeneous　photocatalysts.　Furthermore,　the　application　to　challenging　alkyne　substrates　has　been　demonstrated,　underscoring　the　potential　for　a　broad　range　of　applications　in　pharmaceutical　research　and　synthetic　chemistry.　©　2024　Wiley-VCH　GmbH.