A series of new poly(benzimidazopyrrolone amide) (PPA) copolymers were synthesized by a two-step procedure, which was the solution polycondensation of a novel pyridine-containing tetraamine with various aromatic dianhydrides at a room temperature and cyclization of the resulting prepolymers at a high temperature, respectively. The resulting prepolymers from the solution polycondensation, that is, poly(amide amino acid)s (PAAAs), had inherent viscosities of 0.82-0.91 dL/g; then, tough and flexible PPA films could be successfully prepared by the casting of the PAAA solutions onto a glass substrate followed by thermal curing with a program temperature procedure up to 350 degrees C. The obtained PPA films exhibited not only excellent thermal properties with onset decomposition temperatures in the range 502-521 degrees C, glass-transition temperatures in the range 299-337 degrees C, and residual weight retentions at 700 degrees C in air of 29.1-34.8% but also good mechanical properties with tensile strengths of 102.1-115.9 MPa and elongations at break of 6.8-7.4%. (C) 2008 Wiley Periodicals, Inc.