A series of poly(benzimidazole-imide)s (PBIPIs) derived from different dianhydrides and 2-(3-aminophenyl)-5-aminobenzimidazole (m-BIA) were synthesized via thermal imidization to form flexible films. This series of PBIPIs showed great Tgs ranging from 296 to 484 °C, excellent thermal stability performed in 5% weight loss temperatures (Td5%s) of 502–529 °C in N2 and good mechanical properties (tensile strengths of 89–127MPa, tensile moduli of 2.9–4.1 GPa and elongations at break of 3.9–6.9%). Compared with PIs derived from 6-amino-2-(4-(4-aminophenoxy)phenyl)-1H-benzimidazole (p-BIODA), m-BIA based PBIPI films exhibited higher Tg, and better solubility. Besides, the thermoplastic PBIPI resin (PI-6-PA) derived from 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride (BPADA) and m-BIA exhibited goodmelt processability with high Tg of 273 °C, melt flow index (MFI) of 7.76 g/10 min,

minimum complex viscosity of 11.9 × 103 Pa·s at 402 °C and low melt viscosity ratio of 2.46 at 400 °C.