A series of electron-accepting azaacene-type materials 1-4 with different kinds and degrees of intermolecular interactions were synthesized. Simple modification of the terminal substituents significantly modulated the photophysical and electrochemical properties. The degree of weak intermolecular interaction determined the emergence of a liquid crystalline (LC) phase for each compound. Dipole-dipole interaction, π- π interaction, and van der Waals interaction all contributed to stabilize the LC phase of 1 and 2. The introduction of strong hydrogen bonding interaction enabled the formation of a highly ordered LC phase in 4. Charge-transport properties of 1, 2, and 4 were also investigated.