New tetrazole-fused pi-conjugated molecules were prepared from dibromobenzonitriles by repeated regioselective Sonogashira-Hagihara cross-coupling with acetylenes and intramolecular nucleophilic cyclizations. The conjugated tetracyclic compounds exhibited fluorescence with lifetimes of nanosecond order. From TD-DFT calculations, excited state wavefunctions of compounds indicated that the HOMO-1 -> LUMO and HOMO -> LUMO+1 mainly became the first excited state (S-0 -> S-1) to contribute significantly to light emission.