This manuscript focuses on the influence that the addition of Fe 2+ as electron donor quencher exerts on the photophysics of 2,4,6-triphenylpyrylium (TP + ) depending on the formation or not of supramolecular inclusion complexes with cucurbit[n]uril (n: 7 or 8). 1 H-NMR spectroscopy does not provide evidence supporting the formation of a ternary TP + @CB[n]–Fe 2+ complex. Emission quenching studies indicate that the prevalent deactivation mechanism for the quenching of TP + emission by Fe 2+ is by increasing the ionic strength of the solution, with no evidence for the occurrence of dynamic quenching. Laser flash photolysis indicates that while the triplet excited state of TP + is instantaneously quenched by Fe 2+ in the absence of CB[n], formation of the TP + @CB[n] inclusion complex protects TP + triplet excited state from quenching, an effect that is more pronounced in the case of CB[8] due to the deeper penetration and more complete encapsulation of the heterocyclic pyrylium core inside the larger CB[8] capsule.