A series of five excited-state intramolecular proton transfer (ESIPT) emitters based on a 2-(2′-hydroxyphenyl) benzoxazole (HBO) scaffold, functionalized with a mono-or bis-(trialkylsilyl) acetylene extended spacer are presented. Investigation of their photophysical properties in solution and in the solid-state in different matrix, along with ab initio calculations gave useful insights into their optical behavior. Random lasing studies were conducted on a series of PMMA doped thin films, showing the presence of stimulated emission above the threshold of pumping energy density (ρth ≈ 0.5–2.6 mJ cm−2). In this work, the similarity of four level laser systems is discussed in light of the ESIPT photocycle.