Excited-state intramolecular proton transfer (ESIPT) dyes typically show strong solid-state emission, but faint fluorescence intensity is observed in the solution state owing to detrimental molecular motions. This article investigates the influence of direct (hetero)­arylation on the optical properties of 2-(2′-hydroxyphenyl)­benzoxazole ESIPT emitters. The synthesis of two series of ESIPT emitters bearing substituted neutral or charged aryl, thiophene, or pyridine rings is reported herein along with full photophysical studies in solution and solid states, demonstrating the dual solution-/solid-state emission behavior. Depending on the nature of substitution, several excited-state dynamics are observed: quantitative or partially frustrated ESIPT process or deprotonation of the excited species. Protonation studies revealed that pyridine substitution triggered a strong increase of quantum yield in the solution state for the protonated species owing to favorable quinoidal stabilization. These attractive features led to the development of a second series of dyes with alkyl or aryl pyridinium moieties showing strong tunable solution/solid fluorescence intensity. For each series, ab initio calculations helped rationalize and ascertain their behavior in the excited state and the nature of the emission observed by the experimental results.

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.