Chiral　self-discrimination　plays　a　critical　role　in　supramolecular　chemistry　and　materials　science.　However,　an　ideal　strategy　for　achieving　chiral　self-discrimination　remains　elusive　due　to　the　inevitable　nonspecific　binding　of　incorrect　enantiomers,　and　insufficient　intrinsic　optical　activity　of　chiral　molecules.　Herein,　a　novel　1,1′-binaphthol　(BINOL)　derivative　with　an　imide　group　fused　at　the　peri-position　of　one　naphthol　scaffold　is　developed,　which　combines　the　dual　functionalities　of　aggregation-induced　emission　characteristic　of　BINOLs,　and　high　emission　of　1,8-naphthalimides.　The　multiple　molecular　recognition　between　two　hydroxyl　groups　in　BINOL　units　and　two　carbonyl　groups　in　1,8-naphthalimide　moieties　endows　the　precise　chiral　self-discrimination　behaviors.　As　expected,　the　homochiral　aggregates　exhibit　reversible　phase　transitions,　switching　from　non-emission　to　bright　green　emission　upon　absorption　and　desorption　of　methanol　vapor.　In　contrast,　the　heterochiral　conglomerates　exhibit　irreversible　yellow　emission　changes　due　to　the　impact　of　chiral　self-discrimination.　Such　chiral　self-discrimination-induced　luminescence　vapochromism　can　be　further　applied　to　high-level　anti-counterfeiting　and　data　encryption.　This　work　provides　a　new　perspective　on　smart　chiral　organic　materials　based　on　chiral　self-discrimination.　©　2024　Wiley-VCH　GmbH.