Aromatic poly(amide amine)s (APAAs), as novel high-performance polymers, have been obtained by the condensation polymerization of N,N'-bis(4-bromobenzoyl)-p-phenylenediamine with two different primary aromatic diamines via palladium-catalyzed aryl amination reaction. The structures of the polymers are characterized by means of FTIR, H-1 NMR spectroscopy, and elemental analysis, the results show a good agreement with the proposed structures. DSC and TGA measurements exhibit that polymers possess high glass transition temperature (T-g> 240 degrees C) and good thermal stability with high decomposition temperatures (T-5 > 400 degrees C). These novel polymers also display good solubility. In addition, due to its special structure, APAA-2 is endowed with significantly strong photonic luminescence in N,N-dimethylformamide and good electroactivity. (c) 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 4845-4852