Organic　fluorophores　with　highly　efficient　luminescence　in　both　solution　and　solid　states　have　attracted　significant　attention　due　to　their　ability　to　circumvent　the　limitations　of　aggregation-caused　quenching　and　aggregation-induced　emission　type　molecules.　However,　their　development　and　wide-range　applications　are　hampered　by　extremely　complex　synthetic　methodologies　and　limited　frameworks　with　dual-state　emission　(DSE)　structural　characteristics.　In　sharp　contrast　to　the　reported　luminogens　with　big　and　planar　π　systems　or　highly　conjugated　and　twisted　structures,　we　discovered　novel　three-dimensional　scaffolds　in　one　molecule　to　achieve　DSE.　These　molecules　allowing　for　rapid　access　showed　completely　different　molecular　packing　manners　from　those　of　planar　conjugated　molecules　and　exhibited　excellent　optoelectronic　properties　with　diminished　intermolecular　π−π　stacking　interactions　due　to　steric　hindrance.　Our　findings　should　open　new　avenues　for　designing　DSE　molecules　with　new　frameworks,　which　will　enable　more　successful　development　of　dual-state　emitters　for　their　broad　applications　in　the　future.　©　2023　Wiley-VCH　GmbH.