This　work　proposes　a　σ-π　hyperconjugation　strategy　to　establish　interlayer　charge　transport　channels　(CTC)　in　supramolecular　organic　nanostructures.　A　series　of　ullazine-based　molecular　semiconductors　were　designed　and　synthesized　successfully　by　engineering　end　groups　to　demonstrate　the　σ-π　hyperconjugation　that　unlocks　the　quantum　confinement　of　photogenerated　charges　in　π-conjugated　planes.　Ullazine　grafted　with　tert-butyl　(U-t-Bu)　showed　a　J-cross-stacking　model　in　which　the　cross-stacked　U-t-Bu　molecular　pair　smoothly　glides　along　the　elongated　dimension,　forming　a　Z-schemed　interlayer　CTC　by　σ-π　hyperconjugations　between　C-H　σ-bonds　of　tert-butyl　end　group　and　π-bonds　of　ullazines　in　adjacent　layers　along　the　stacking　dimension.　Consequently,　upon　photoexcitation　of　ullazine-based　supramolecular　nanoaggregates　in　aqueous　solution,　the　formed　Frenkel　excitons　are　dissociated　to　charge-separated　excitons　by　the　interlayer　charge　separation　channels,　undergoing　an　ultrafast　charge　transfer　within　0.58　ps　and　an　ultrafast　charge　separation　within　0.67　ps.　The　Z-schemed　charge　separation　between　adjacent　layers　leads　to　a　significantly　enhanced　hydrogen　yield　over　U-t-Bu/PVP/Pt,　with　a　hydrogen　evolution　rate　of　369.9　μmol·g-1·h-1　and　an　apparent　quantum　yield　of　1.46%　at　420　nm.　It　is　3.8-fold　larger　than　that　of　ullazine　modified　with　methoxy　(U-OMe),　without　the　σ-π　hyperconjugation.　©　2025　American　Chemical　Society.