A series of novel benzimidazole-containing aromatic polyimides were prepared from synthesized 5,4'-diamino-2-phenyl benzimidazole (DAPBI), and commercial dianhydrides by the conventional two-step polymerization. The obtained films were amorphous and could afford flexible, transparent, and tough films with excellent thermal and mechanical properties. They showed high levels of tension strength of up to 234 MPa, modulus of up to 5.6 GPa without any stretching. According to thermal stability measurements, the glass-transition temperatures of the polymers were observed between 329 and 425 degrees C. The 5% weight-loss temperatures of most polyimides were above 600 degrees C in nitrogen. Excellent properties of these polyimides were proved to be attributed to the rigid-rod structure and hydrogen bond of inter-macromolecular. SAXS and SEM results showed self-molecular orientation caused the formation of rod-like extended conformations. It was demonstrated that high degree of supramolecular order led to the increase of thermal stability and mechanical properties of the polyimide films. (C) 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2024-2031, 2009