Despite　the　unique　advantages　of　non-planar　conjugated　molecules　in　promoting　charge　separation　through　their　twisted　conformations　and　weakened　intermolecular　interactions,　a　systematic　understanding　of　their　structure-performance　relationships　in　photocatalysis　remains　lacking.　This　work　proposed　an　intramolecular　torsional　angle　regulation　strategy　to　establish　non-planar　conjugate　stacking　architectures　for　optimized　interlayer　charge　separation　in　supramolecular　organic　catalysts.　A　series　of　ullazine-pyridine　supramolecular　semiconductors　(o-U-Py,　m-U-Py,　p-U-Py)　were　designed　to　achieve　favorable　packing　arrangements　that　facilitate　the　liberation　of　electrons　from　Coulombic　confinement　through　the　precise　regulation　of　nitrogen　atom　positions　(ortho,　meta,　para)　on　the　pyridine　moiety.　The　meta-substituted　m-U-Py　derivative,　which　exhibits　the　most　pronounced　torsion　angle　of　38.5°,　demonstrates　optimal　interlayer　conjugation　projection　efficiency　and　features　a　nearest　N-N　active　site　distance　of　4.7　Å.　These　synergistic　features　promoted　photogenerated　charge　separation　through　intermolecular　built-in　electric　fields,　culminating　in　the　lowest　recorded　exciton　binding　energy　of　81.8　meV　and　ultrafast　charge　separation　kinetics　with　τCS　≈　0.43　ps.　The　superior　charge　separation　efficiency　empowered　m-U-Py　to　demonstrate　exceptional　photocatalytic　hydrogen　evolution　performance　under　visible　light　irradiation,　achieving　an　exceptional　production　rate　of　1807.8　μmol·g−1·h−1,　representing　5-fold　and　2.5-fold　enhancements　over　o-U-Py　and　p-U-Py　respectively,　accompanied　by　an　apparent　quantum　yield　of　1.39　%　at　420　nm.　This　work　provides　a　novel　molecular　design　strategy　for　developing　efficient　non-planar　conjugated　photocatalysts.　©　2025　Elsevier　B.V.