A pair of 2D chiral frameworks, R-Ag5-1 and S-Ag5-1, with orange fluorescence were successfully synthesized. They were transformed to a thermodynamically favored denser stacking, R-Ag5-3 and S-Ag5-3, accompanied by a change in the luminescence and activating the CPL signal. The capture and structural determination of the intermediates (R-Ag5-2 and S-Ag5-2) reveal that the coordination instability of Na+ ions is the main cause of this transition.