<p>Chiral recognition through fluorescence changes enables the rapid and sensitive determination of enantiomers. However, the rational design and synthesis of fluorescent probes for efficient chiral recognition remain a challenge. Here we present a novel platform for chiral recognition based on zero-dimensional hybrid copper halides with unique symmetry-dependent properties. The use of mesomeric 1,2-diaminocyclohexane (DACH) ligands promotes the formation of centrosymmetric, non-luminescent Cu₂I₆⁴⁻ units. The incorporation of enantiopure <i>S</i>- or <i>R</i>-DACH ligands into these mesomeric compounds breaks their symmetry, spontaneously transforming them into chiral compounds and generating Cu₄I₆²⁻ units that exhibit intense circularly polarized luminescence. Additionally, introducing opposite chiral ligands into these chiral compounds leads to the formation of racemic, non-luminescent CuI₃²⁻ units, whereas the addition of same-chirality ligands preserves the structure and optical properties of the chiral Cu₄I₆²⁻ units. This enantioselective response by utilizing symmetry-dependent optical properties offers a pathway toward advanced chiral sensing technologies.</p>