Polymer film capacitors are ubiquitous in modern electronics and electric systems, but the relatively low working temperatures of polymer dielectrics limit their application in next-generation capacitors. The currently reported high-temperature polymer dielectrics rely on the construction of nanocomposites with wide band gap fillers and cross-linked networks to achieve high breakdown strength and high efficiencies. However, generating the optimal chain structure with intrinsic great high-temperature capacitive properties using a one-component polymer is still challenging. Herein, a giant discharged energy density in neat polymer has been demonstrated in a series of linear poly(arylene ether amide) (PNFA) at 150 °C, which greatly surpass all the current free-standing dielectric polymer films measured in 10 Hz. The maximum discharged energy density with efficiency above 90% of the PNFA is 2.7 J cm–3, which is about 3 times that of the state-of-the-art commercial high-temperature polymer films. The architectures of the amorphous polymers have been identified by synchrotron X-ray diffraction combined with density functional theory calculations. The origins of superior high-temperature capacitive properties are traced to the increased packing density by the curly-packed chain structure. In addition, the reported polymer could be produced using existing industrial-grade processes, which are economical and practical for large-scale applications.