Four novel pyrene-fused asymmetrical twistacenes (1–4) containing heteroatoms in the main frameworks were synthesized and their structures are characterized by using 1 HNMR, 13 C NMR and mass spectrometry. Single crystal X-ray analysis shows that compound 1 has a twisted structure with the torsion angle of 26.39° between pyrene moiety and naphthalene unit, and the terminal benzenedithiol group fold out of the naphthalene plane with dihedral angle of 53.10°. Moreover, the effect of heteroatoms on their optical and electrochemical property was studied in detail. The fabricated devices based on 3 and 4 can produce steady photocurrent upon irradiation of a halogen lamp.