Aromatic poly(amide amine)s (APAAs), as novel highperformance polymers, have been obtained by the condensation polymerization of N,N’-bis(4-bromobenzoyl)-p-phenylenediamine with two different primary aromatic diamines via palladiumcatalyzed aryl amination reaction. The structures of the polymers are characterized by means of FTIR, 1H 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 (Tg > 240 C) and good thermal stability with high decomposition temperatures (T5 > 400 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.