In this study, we have demonstrated how thermally activated molecular rotation can modulate chiroptical properties, such as circularly polarized luminescence (CPL), in the solid state, using the example of crystalline chiral binuclear NHC Au(I) complexes 1-R and 1-S. This enantiomeric pair of NHC Au(I) complexes exhibits distinct chiral conformations with C2 symmetry and thermally activated rotational motion of the phenyl groups in the crystalline state, as confirmed by SCXRD and solid-state 2 H NMR studies. The obtained crystalline complexes display a good quantum yield of 30% and luminescence dissymmetry factors of ±5-8 × 10 -3 at room temperature in the solid state. Moreover, the combination of molecular dynamics, intrinsic chirality, and emissive features of the studied crystalline complexes results in the emergence of thermo-responsive CPL properties, with a dramatic 4-fold enhancement of CPL intensity and up to ~50% increase of luminescence dissymmetry factor values (glum) upon cooling.