Efficient　artificial　photosynthesis　of　disulfide　bonds　holds　promises　to　facilitate　reverse　decoding　of　genetic　codes　and　deciphering　the　secrets　of　protein　multilevel　folding,　as　well　as　the　development　of　life　science　and　advanced　functional　materials.　However,　the　incumbent　synthesis　strategies　encounter　separation　challenges　arising　from　leaving　groups　in　the　-S-S-　coupling　reaction.　In　this　study,　according　to　the　reaction　mechanism　of　free-radical-triggered　-S-S-　coupling,　light-driven　heterojunction　functional　photocatalysts　are　tailored　and　constructed,　enabling　them　to　efficiently　generate　free　radicals　and　trigger　the　coupling　reaction.　Specifically,　perovskites　and　covalent　organic　frameworks　(COFs)　are　screened　out　as　target　materials　due　to　their　superior　light-harvesting　and　photoelectronic　properties,　as　well　as　flexible　and　tunable　band　structure.　The　in　situ　assembled　Z-scheme　heterojunction　MAPB-M-COF　(MAPbBr(3)　=　MAPB,　MA(+)　=　CH3NH2+)　demonstrates　a　perfect　trade-off　between　quantum　efficiency　and　redox　chemical　potential　via　band　engineering　management.　The　MAPB-M-COF　achieves　a　100%　-S-S-　coupling　yield　with　a　record　photoquantum　efficiency　of　11.50%　and　outstanding　cycling　stability,　rivaling　all　the　incumbent　similar　reaction　systems.　It　highlights　the　effectiveness　and　superiority　of　application-oriented　band　engineering　management　in　designing　efficient　multifunctional　photocatalysts.　This　study　demonstrates　a　concept-to-proof　research　methodology　for　the　development　of　various　integrated　heterojunction　semiconductors　for　light-driven　chemical　reaction　and　energy　conversion.