Photoluminescence (PL) modulation in molecular or supramolecular level can provide potentials for high density data processing by combining chemical and photonic input/output signals together in a nanoscale integrated system. Herein, a PL-responsive supramolecular coordination cage has been applied for interactions with redox-active guests. PL signals of the cage can be switched and modulated by adding/retracting Fc derivatives or converting TTF into different oxidation states via chemical or photochemical pathways. As a result, reversible or stepwise PL switches are displayed by these host-guest systems due to occurrence of PET (photoinduced electron-transfer) or FREnT (fluorescence resonance energy transfer) processes, providing nano-device models for off/on logic gate or memristor-like sequential Boolean operation functions.