A new family of thiophene-fused thiopyrylium salts has been synthesized via Lewis-acid-induced Rieche formylation, followed by an intramolecular Friedel-Crafts cyclization of a series of diarylthioethers. Moreover, in the case of diarylthioethers that bear formyl groups, Lewis-acid-promoted intramolecular cyclizations afforded novel thiophene-fused bisthiopyrylium salts in good yield. The electronic structures of the new compounds were determined experimentally by NMR and UV-vis absorption spectroscopy and theoretically investigated by density functional theory calculations. The results of our examinations revealed effective conjugation of the π-electrons over the entire linearly fused heteroacene framework.