Polyimides (PIs) with super heat‐resistance and ultralow coefficient of thermal expansion (CTE) are required urgently to employ as plastic substrates in flexible‐display devices. To attain the target properties, we designed and synthesized a novel bibenzimidazole diamine characterized in having a N‐phenyl group, namely 1‐phenyl‐2,2′‐bibenzoimidazole‐5,5′‐diamine (PhDABZ), and focused on an aromatic poly(benzimidazole imide) series derived from 1,2,4,5‐benzenetetracarboxylic (PMDA). Incorporating bibenzimidazole and N‐substituent effectively increase the interchain interaction and chance for flexible film formation, which provides the PIs with high glass‐transition temperature (Tg > 480 °C) and dimensional stability (CTE < 10 ppm K−1). These data provide a feasible method to achieve higher thermal properties of PIs.

Colorless polyimides (CPIs) with superheat resistance and low coefficient of thermal expansion (CTE) are required urgently to employ as plastic substrates in flexible‐display devices. To attain the target properties, 2‐(2‐methyl‐4‐(4‐aminobenzamido)phenyl)‐5‐(4‐aminobenzamido)‐N‐phenylbenzimidazol (AB‐MPBZ) that contains biamide was synthesized, and its homo‐ and co‐polyimides were prepared with 1,2,4,5‐cyclohexanetetracarboxylic dianhydride (HPMDA) and cyclobutane‐1,2,3,4‐tetracarboxylic dianhydride (CBDA). The crank‐shaft‐like amide groups effectively increases the linearity and stiffness of polymer segments, providing CPI films with low CTE. On the basis, the CBDA based poly(benzimidazole imide) (PBII) series with dense interchain packing exhibits further reduced CTE down to 22 ppm K−1 and increased glass‐transition temperature (Tg) up to 404 °C. Such good thermal properties indicate that the resultant copolyimides have potential applications as colorless flexible substrates. These provide a feasible approach to balance thermal and optical performance of polyimides.