Controlling the spatial distribution of photoluminescent molecules within constrained microenvironments remains a fundamental challenge for enhancing their photophysical properties. Herein, we focus on the differential adsorption behaviors of enantiopure and racemic octahedral metal complexes on clay surfaces as a means to amplify these properties, including circularly polarized luminescence (CPL). Two iridium(III) complexes exhibiting Δ and Λ chirality, [Ir(ppy) 2 (phen)](PF 6 ) (
Ir1-PF
6
) and [Ir(piq) 2 (phen)](PF 6 ) (
Ir2-PF
6
), were employed as chiral luminophores. Investigations into the adsorption behavior of these complexes on colloidal clay revealed that the Ir1 + cation, which possesses pseudo- C3 symmetry, displays UV–vis, photoluminescence (PL), and circular dichroism (CD) spectra distinctly different from those of the free complex in solution. Conversely, no such spectral changes were observed for the bulkier and lower-symmetry Ir2 + complex in the clay colloidal suspensions. These spectral changes in Ir1 + are attributed to its conformational fixation on the clay surface and the restricted molecular motion, which effectively suppress nonradiative decay processes. Specifically, structural matching between the ligands of Ir1 + and the hexagonal cavities of the clay surface likely leads to rigid stabilization. In contrast, the bulkier ligands of I Ir2 + likely prevent such rigid fixation. Furthermore,
Ir1-PF
6
and
Ir2-PF
6
with the same absolute configuration (Δ or Λ) exhibited opposite CPL signs in solution. This inversion is attributed to the ligand-dependent changes in orbital topologies, which reverse the transition dipole moments. In colloidal suspensions, the CPL intensity of Ir1 + increased—an effect similarly attributed to conformational fixation—whereas that of Ir2 + decreased. Remarkably, this enhancement of CPL intensity of Ir1 + upon clay adsorption is highly reminiscent of cryogenic cooling. These results demonstrate that utilizing clay nanosheets as structural scaffolds is a powerful strategy for transforming molecules with weak inherent chiroptical properties into highly functional chiral luminescent materials.