High dielectric permittivity materials are much desirable in the electric industry. Filling polymer matrix with conductive powders to form percolative composites is one of the most promising methods to achieve high dielectric permittivity. However, they do not always provide high mechanical properties and thermal stability, which seriously limit their applications. In this study, we present the preparation of functional core–shell structured silver nanowires/polyimide (AgNWs/PI) hybrid film with high dielectric permittivity and low loss dielectric. The core–shell structure of AgNWs was characterized by transmission electric microscopy. The dynamical mechanical analysis showed that AgNWs/PI hybrid films had relative high dynamic mechanical properties with storage modules over 1 Gpa. Moreover, the hybrid films exhibited excellent thermal stability with 5 % weight-loss temperature above 500 °C. The dielectric properties of the carbon-coated AgNWs hybrid films were remarkably improved. The maximum dielectric permittivity of hybrid films is 126 at 102 Hz, which was 39 times higher than that of pure PI matrix, while the dielectric loss of that is still remained at a low value. This study showed a new method to improve the dielectric, dynamic mechanical and thermal properties of films.