Binaphthyl-based　chiral　organic　molecules　have　attracted　considerable　attention　due　to　their　potential　in　circularly　polarized　luminescence　(CPL).　In　this　study,　three　pairs　of　enantiomerically　pure　binaphthyl　derivatives　(R/S-1,　R/S-2,　and　R/S-3)　were　synthesized,　and　their　optical　properties　were　systematically　investigated　in　both　the　amorphous　and　crystalline　states.　Notably,　the　crystalline　forms　exhibited　significantly　enhanced　CPL　activity　compared　to　their　amorphous　counterparts,　with　R/S-3　showing　a　nearly　10-fold　increase　in　|glum|.　Single-crystal　X-ray　diffraction　analysis　revealed　that　enhanced　intermolecular　interactions　and　highly　ordered　21-helical　packing　promote　efficient　exciton　migration　and　chiral　amplification,　accounting　for　the　improved　CPL　performance.　This　work　provides　new　insights　into　CPL　enhancement　via　crystalline-state　engineering　and　offers　guidance　for　developing　practical　CPL-active　materials.　©　2025　American　Chemical　Society.