2‐(2’‐Hydroxyphenyl)benzazole (HBX) fluorophores are well‐known excited‐state intramolecular proton transfer (ESIPT) emitters largely studied for their synthetic versatility, photostability, strong solid‐state fluorescence and ability to engineer dual emission, thus paving the way to applications as white emitters, ratiometric sensors, and cryptographic dyes. However, they are heavily quenched in solution, due to efficient non‐radiative pathways taking place as a consequence of the proton transfer in the excited‐state. In this contribution, the nature of the heteroring constitutive of these rigidified HBX dyes was modified and we demonstrate that this simple structural modification triggers major optical changes in terms of emission color, dual emission engineering, and importantly, fluorescent quantum yield. Investigation of the photophysical properties in solution and in the solid state of a series of ethynyl‐TIPS extended HBX fluorophores, along with ab initio calculations demonstrate the very promising abilities of these dyes to act as bright dual‐state emitters, in both solution (even in protic environments) and solid state.

Explanation of the experimental triple emission with theoretical tools requires advanced solvent models.