Aromatic polyimide has good mechanical properties and high-temperature resistance. Based on this, benzimidazole is introduced into the main chain, and its intermolecular (internal) hydrogen bond can increase mechanical and thermal properties and electrolyte wettability. Aromatic dianhydride 4,4'-oxydiphthalic anhydride (ODPA) and benzimidazole-containing diamine 6,6'-bis [2-(4-aminophenyl)benzimidazole] (BAPBI) were synthesized by means of a two-step method. Imidazole polyimide (BI-PI) was used to make a nanofiber membrane separator (NFMS) by electrospinning process, using its high porosity and continuous pore characteristics to reduce the ion diffusion resistance of the NFMS, enhancing the rapid charge and discharge performance. BI-PI has good thermal properties, with a Td5% of 527 °C and a dynamic mechanical analysis Tg of 395 °C. The tensile strength of the NFMS increased from 10.92MPa to 51.15MPa after being hot-pressed. BI-PI has good miscibility with LIB electrolyte, the porosity of the film is 73%, and the electrolyte absorption rate reaches 1454%. That explains the higher ion conductivity (2.02 mS cm) of NFMS than commercial one (0.105 mS cm). When applied to LIB, it is found that it has high cyclic stability and excellent rate performance at high current density (2 C). BI-PI (120 Ω) has a lower charge transfer resistance than the commercial separator Celgard H1612 (143 Ω).