A　multicomponent　heterogeneous　semiconductor　photocatalytic　sulfinylsulfonylation　of　alkenes　with　alkyl　iodides　and　SO2　was　displayed　under　mild　metal-free　conditions　by　using　boron　carbonitride　(BCN)　as　the　alternative　photocatalyst.　This　approach　has　resulted　in　the　production　of　a　wide　range　of　structurally　diverse　sultine　products　in　moderate　to　high　yields,　using　readily　available　starting　materials　including　alkyl　iodides　and　olefins　with　broad　functional　group　tolerance.　The　method　is　also　suitable　for　the　late-stage　functionalization　of　complex　bioactive　molecules.　A　radical-polar　crossover　cyclization　(RPCC)　process　was　proposed　based　on　mechanistic　studies.