Polymeric　carbon　nitride　(PCN)　is　a　promising　hotspot　metal-free　material　for　artificial　photosynthesis,　solar　energy　conversion,　and　photo　degradation　of　pollutant,　hence　predicting　unsatisfactory　photocatalytic　efficiency　due　to　fast　charge　recombination.　Here,　we　implemented　a　remediation　approach　to　fuel　its　catalytic　performance　by　interpretation　of　a　sulfur　rich-material,　ie,　trithiocyanuric　acid　(TTCA)　in　the　framework　of　PCN　by　traditional　one　facile　protocol　called　copolymerization　(molecular　assembled)　under　nitrogen　at　550°C.　Results　demonstrate　that　the　integration　of　TTCA　comonomer　into　the　triazine　oligomers　of　PCN　widens　the　specific　surface　area,　extends　the　lifetime　of　photoexcited　charge　carriers,　speeds　up　the　rate　of　photogenerated　electrons　optimized　from　lower　energy　state　toward　high　energy　state,　lowers　the　rate　of　charge　recombination　and　band　gap,　and　modulates　its　electronic　structure　and　optical　properties　in　a　regular　fashion　as　compared　with　pristine　PCN.　Ultimately,　due　to　aforementioned　modification,　the　copolymerized　PCN　semiconductor　predicts　superior　photocatalytic　properties　of　hydrogen　energy　production　about　7　times　higher　than　that　of　pristine　PCN　from　the　water　splitting　system.　©　2019　John　Wiley　&　Sons,　Ltd.