A new high-performance material, poly(sulfone-imide) was prepared by Ni(0)-catalyzed coupling of aromatic dichlorides containing imide structure and 4,4'-dichlorodiphenylsulfone. The copolymers were produced with high yield and moderate to high inherent viscosities of 0.52–1.13 dL/g. Wide-angle X-ray diffractograms revealed that the polymers were amorphous. Most of the polymers exhibited good solubility and could be readily dissolved in various solvents such as N-methyl-2-pyrrolidinone(NMP) and N, N-dimethylacetamide (DMAc). These polysulfone-imides had glass-transition temperatures between 317 and 345 °C and 10% weight loss temperatures in the range of 450–476 °C in nitrogen atmosphere. The tough polymer films, obtained by casting from cresol solution, had a tensile strength range of 21–158 MPa and a tensile modulus range of 2.1–3.3 GPa.