The invention provides a benzimidazole-substituted polyimide, a preparation method thereof, a benzimidazole-substituted polyimide film, and a preparation method and an application of the film, and belongs to the technical field of polyimide materials. The glass transition temperature of the benzimidazole-substituted polyimide film is 328-431 DEG C, the 5% thermal decomposition temperature is 498-537 DEG C, the tensile strength is 69-190 MPa, the tensile modulus is 3.5-6.2 GPa, the water absorption rate is 1.12-1.78%, the thermal expansion coefficient is 2.5-48.0 ppm/K, and the film is thermally soluble in m-cresol, N-methylpyrrolidone, dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide and tetrahydrofuran organic solvents. The benzimidazole-substituted polyimide film providedby the invention has the advantages of high thermal stability, good dimensional stability, low water absorption rate, excellent mechanical properties, and good solubility in organic solvents.