In this study, a series of porous polyimide films containing benzimidazole units were prepared through a phase separation process. The dibutyl phthalate was selected as porogen. The copolyimides were prepared by the reaction of 3,3′,4,4′-benzophenonetetracarboxylic dianhydride with two diamines of 2-(4-aminophenyl)-5-aminobenzimidazole (BIA) and 4,4′-diaminodiphenyl ether with various molar ratios. The resultant porous polyimide films exhibit optimum cell-size distributions. The effects of BIA on morphology, mechanical, and thermal properties of the porous films were explored. It was found that as the BIA content reached up to 30 mol%, the porous copolyimide film demonstrates remarkable thermal stability and admirable mechanical properties with the glass transition temperature of 294°C, 5% weight loss temperature in argon flow up to 545°C, and a tensile strength of 48 MPa. The incorporation of BIA into the polyimide chains brought the highly rigid structures and strong intermolecular interactions, resulting in the enhancement in the thermal stability and the mechanical properties.