A novel large thiophene-fused polycyclic aromatics 1 based on pyrene 5 has been synthesized, and its structure was confirmed by 1H NMR, 13C NMR, MS, UV-vis and elemental analysis. The key steps of the synthesis involved the Stille cross-coupling reaction and followed by selective β-β oxidative cyclization of pendant thienyl rings by FeCl3 under mild conditions.