AbstractWe have investigated the spectroscopic properties (absorption spectra, emission spectra, emission lifetimes) of three triads in CH2Cl2: C2‐M‐C2, C343‐M‐C343, and C2‐M‐C343, in which M is a shape‐persistent macrocyclic hexagonal backbone composed of two 2,2′‐bipyridine (bpy) units embedded in opposing sides, and C2 and C343 are coumarin 2 and coumarin 343, respectively. All the components are strongly fluorescent species (Φ=0.90, 0.79, and 0.93 for M, C2, and C343, respectively, as established by investigating suitable model compounds). In each triad excitation of M leads to almost quantitative energy transfer to the lowest coumarin‐localised excited state. Upon addition of acid, the two bpy units of the M component undergo independent protonation leading to monoprotonated (e.g., C2‐M⋅H+‐C2) and diprotonated (e.g., C2‐M⋅2 H+‐C2) species. Further addition of acid leads to protonation of the coumarin component so that each triad is involved in four protonation equilibria. Protonation causes strong (and reversible, upon addition of base) changes in the absorption and fluorescence properties of the triads because of inversion of the excited‐state order and/or the occurrence of electron‐transfer quenching processes.