AbstractAll-organic high dielectric materials are highly required in the field of modern electronic industry and energy storage. In this work, all-organic polyimide/polysulfone composite films with different amounts of PSF (PI/PSF-X) were prepared by in situ polymerization followed by film casting and thermal treatment. The dielectric, mechanical and thermal properties of these PI/PSF-X composite films are characterized by dielectric measurement, tensile test, thermogravimetric analysis and dynamic mechanical analysis. The results suggest that the PI/PSF-X composite films have good dielectric properties, good mechanical properties and excellent thermal properties, which are suitable for applications in electronic devices in harsh environments, especially in high-temperature environments.