A series of novel substituted 1,3,4-oxadiazole derivatives containing pyrido[1,2-a]benzimidazole moiety were synthesized and characterized using FTIR, 1 H NMR, 13 C NMR, and HRMS. An efficient tandem reaction was employed as a key step in constructing the pyrido[1,2-a]benzimidazole moiety under very mild condition. The structure of compound 4a was established by X-ray crystallography. The UV–vis absorption and fluorescence spectral characteristics of these compounds were investigated in several solvents. Compounds 4a–i display similar absorptions, with absorption peaks ranging from 330 to 339nm in acetonitrile, while the absorption maxima of compound 4j bearing a diphenylamino group on the benzene ring is red-shifted distinctly to 377nm due to the strong electron-donating property of its substituent and extended π-conjugated system. All these target heterocyclic compounds present blue-green emissions (461–487nm) in dilute solutions and show high quantum yields of fluorescence (Ф PL =0.65−0.99) in dichloromethane.