Novel tricyclic fluorophores were obtained from 2-aryl-[1,2,4]triazolo[1,5-c]quinazoline-5(6H)-ones through chlorodesoxygenation and subsequent Suzuki–Imamura cross-coupling reactions. Their π-extended analogues were synthesized from 5-(4-bromophenyl)-[1,2,4]triazoloquinazolines. The structure of target fluorophores was confirmed by X-ray single crystal diffraction. Photophysical properties in solutions and solid state were studied. 5-Aminoaryl-substituted [1,2,4]triazolo[1,5-c]quinazolines revealed bright blue fluorescence in toluene (ΦF > 95%), which can be tuned by solvent polarity, the electronic nature and rigidity of the donor fragment, the π-spacer length, and the annelation pattern. Intramolecular charge transfer (ICT) behaviour was demonstrated using both experimental and theoretical data. Distinct acid-induced spectral and fluorescence changes upon protonation were observed for diethylamino-containing derivatives, indicating their potential applicability as dual-mode (polarity and pH) molecular sensors.