Precise　and　efficient　management　of　disulfide　bonds　will　offer　multiple　merits　for　the　development　of　organosulfur　chemistry,　pharmacology,　and　life　sciences.　However,　the　current　S-S　coupling　synthesis　strategy　encounters　bottlenecks　in　conforming　to　efficient　separation　of　products,　which　limits　its　industrial-scale　application.　In　view　of　the　superoxide　radical-triggered　reaction　mechanism　of　S-S　coupling,　this　study　demonstrates　a　multifunctional　in　situ-assembled　0D/1D　S-scheme　heterojunction　photocatalyst　(MAPB-T-COF)　constructed　by　MAPbBr3　quantum　dots　and　imine　covalent　organic　framework　(COF)　nanowires　under　the　guidance　of　band　engineering　management.　MAPB-T-COF　exhibits　a　superior　photocatalytic　performance　in　the　conversion　of　4-methylbenzenethiol　(4-MBT)　to　p-tolyl　disulfide　(PTD)　under　blue　LED　illumination.　Specifically,　it　achieves　an　impressive　100%　yield　with　a　record　photon　quantum　efficiency　as　high　as　12.76%,　as　well　as　universal　availability　for　various　derivatives,　rivaling　all　the　incumbent　similar　reaction　systems.　This　study　not　only　highlights　the　effectiveness　and　merits　of　nanoscale　S-scheme　heterojunction　photocatalysis　for　the　S-S　coupling　reaction　but　also　achieves　a　perfect　trade-off　between　high　quantum　efficiencies　and　strong　chemical　redox　potentials.　In　addition,　the　free　radical　that　triggers　the　reaction　was　monitored　in　situ　by　an　electron　paramagnetic　resonance　(EPR)　instrument,　which　provided　meaningful　insights　into　the　reaction　mechanism.　This　study　may　inspire　the　development　of　photoelectric　conversion　devices,　photoelectrodes,　and　photocatalysts　utilizing　nanoscale,　low-dimensional　heterojunctions.　©　2023　American　Chemical　Society.