A series of poly(N-arylene benzimidazole ether imide) copolymers PEIBIs were prepared from 1H,3′H-5,5′-bis-benzimidazole, bisphenol-A and 4,4′-bis(4-fluorophthalimido)diphenyl ether by nucleophilic displacement polymerization. The resulting copolymers PEIBI(10–90) demonstrated moderate to good solubility in polar aprotic solvents and high glass transition temperatures (Tgs) of 228–336°C, good thermal stability with 10% weight loss temperatures in the range of 503–548°C. All copolymer films showed good mechanical properties with tensile strengths of 101–130 MPa, tensile moduli of 3.3–4.0 GPa, elongations at break of 5–7%, and also presented low water uptake (0.15–0.34%). The wide-angle X-ray diffraction results revealed the amorphous nature of copolymers. The copolymer PEIBI-80 showed good balance in solubility, thermal and mechanical properties.