To develop the polyimide (PI) which is closely matched to the coefficient of the thermal expansion (CTE) of copper, a series of PIs are prepared from 5,4′-diamino-2-phenyl benzimidazole (DAPBI), 4,4′-diaminodiphenyl ether (ODA), and 3,3′,4,4′-benzophenonetetracarboxylic dianhydride (BTDA) using a sequential copolymerization, blade coating, and thermal imidization process. The physical properties of the PIs are effectively regulated and optimized by adjusting the ratio of the rigid DAPBI and flexible ODA components. By increasing the DAPBI content, thermal stability, dimensional stability, and mechanical properties, the resultant polymer is enhanced. PI-80 exhibits an excellent comprehensive performance, a glass transition temperature of 370 °C, and a tensile strength of 210 MPa. Furthermore, the CTE as calculated in the range 50–250 °C is ca. 19 ppm/K, which is equal to that of copper. A highly dimensionally stable, curl-free, and high T-style peel strength (6.4 N/cm) of copper/PI laminate was obtained by casting the polyamic acid onto copper foil (13 μm) and thermally curing at 360 °C, which indicates that it has the potential to be applied as an electronic film for flexible displays and flexible printed circuit boards. A structural rationalization for these remarkable properties is also presented.