Novel aromatic polyamides have been prepared by a combination of diacids containing preformed benzimidazole rings and aromatic diamines. By the phosphorylation method of polycondensation, polymers of high molecular weight (inherent viscosities between 0.81 and 2.13 dL/g) were obtained, which showed good solubility in polar aprotic solvents. The combination of aromatic amide linkages and benzimidazole rings along the polymer chain endowed the polymers with high thermal resistance and excellent mechanical properties. Glass transition temperatures fell in the range of 290-330 degrees C as measured by differential scanning calorimetry, and initial decomposition temperatures under nitrogen were over 480 degrees C as measured by then mogravimetric analysis. Some polymer films showed outstanding tensile strength (over 150 MPa) and moduli (up to 5 GPa). The presence of benzimidazole rings in the current polyamides greatly enhanced their hydrophilicity in comparison with classical wholly aromatic polyamides; thus, although aromatic polyamide films normally show water sorption values of only 4-8%, some of the current poly(benzimidazole amide)s show water sorption up to 19% in a 65% relative humidity atmosphere. (c) 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 7566-7577, 2008