Molecules that can exist in multiple states with the possibility of toggling between those states based on different stimuli have potential for use in molecular switching or sensing applications. Multimodal chemical or photochemical oxidative switching of an antioxidant-substituted resorcinarene macrocycle is reported. Intramolecular charge-transfer states, involving hemiquinhydrones are probed and these interactions are used to construct an oxidation-state-coupled molecular switching manifold that reports its switch-state conformation via striking variation in its electronic absorption spectra. The coupling of two different oxidation states with two different charge-transfer states within one macrocyclic scaffold delivers up to five different optical outputs. This molecular switching manifold exploits intramolecular coupling of multiple redox active substituents within a single molecule.