Compared to electrochemical energy devices such as batteries and supercapacitors, dielectric film capacitors have greater power densities and faster charging and discharging rates and are the essential components in power electronics. [4][5][6] Dielectric polymers possess unique features in comparison to their ceramic counterparts, including high breakdown strength, low dielectric loss, facile preparation, and graceful failure mechanism, which make them the materials of choice for scalable high-energy-density capacitors. [7][8][9][10][11] More recently, there is an urgent demand for dielectric materials capable of operating efficiently at elevated temperatures, e.g., 150 °C, in advanced electronics, electrified vehicles, and aerospace power systems. However, dielectric polymers are limited to relatively low working temperatures. [11][12][13][14][15] For example, the operation temperature of biaxially oriented polypropylene (BOPP), the industrial benchmark dielectric polymer, is well below 105 °C under the applied electric fields. [15] A variety of innovative approaches, including the incorporation of wide bandgap inorganic fillers, [16][17][18] deposition of ceramic coatings onto polymer films, [19][20][21] addition of high-electronaffinity molecular semiconductors, [22] and utilization of multilayer-structured films, [23][24][25] have been developed to improve the high-temperature capacitive performance of dielectric polymers. While these approaches are effective in hindering electrical conduction and reducing energy loss at high fields and elevated temperatures, the energy densities of the current high-temperature dielectric composites are limited (below 4 J cm −3 in most cases) owing to relatively low dielectric constant (K) values of the fillers, such as ≈3.5-4 of SiO 2 and boron nitride nanosheets (BNNSs) [16,26] and ≈7.9-10 of Al 2 O 3 . [26] On the other hand, the direct introduction of high-K inorganic fillers, such as TiO 2 with a K of 110 (ref. [27]) and BaTiO 3 with a K of ≈3000 (ref. [28]), into dielectric polymers with the goal of increasing the energy density has yielded very high energy loss and largely reduced chargedischarge efficiency (η) with increasing applied field and temperature. [29,30] For instance, at an applied field of 400 MV m −1 , the η of the polyimide composites with 1 vol% BaTiO 3 nanofibers is only 55% at 150 °C versus 92% at 25 °C. [30] Herein, we present High-energy-density polymer dielectrics capable of high temperature operation are highly demanded in advanced electronics and power systems. Here, the polyetherimide (PEI) composites filled with the core-shell structured nanoparticles composed of ZrO 2 core and Al 2 O 3 shell are described. The establishment of a gradient of the dielectric constants from ZrO 2 core and Al 2 O 3 shell to PEI matrix gives rise to much less distortion of the electric field around the nanoparticles, and consequently, high breakdown strength at varied temperatures. The wide bandgap Al 2 O 3 shell creates deep traps in the composites and thus yields ...