Flexible dielectrics operable under simultaneous electric and thermal extremes are critical to advanced electronics for ultrahigh densities and/or harsh conditions. However, conventional high-performance polymer dielectrics generally have conjugated aromatic backbones, leading to limited bandgaps and hence high conduction loss and poor energy densities, especially at elevated temperatures. A polyoxafluoronorbornene is reported, which has a key design feature in that it is a polyolefin consisting of repeating units of fairly rigid fused bicyclic structures and alkenes separated by freely rotating single bonds, endowing it with a large bandgap of ≈5 eV and flexibility, while being temperature-invariantly stable over -160 to 160 °C. At 150 °C, the polyoxafluoronorbornene exhibits an electrical conductivity two orders of magnitude lower than the best commercial high-temperature polymers, and features an unprecedented discharged energy density of 5.7 J cm-3 far outperforming the best reported flexible dielectrics. The design strategy uncovered in this work reveals a hitherto unexplored space for the design of scalable and efficient polymer dielectrics for electrical power and electronic systems under concurrent harsh electrical and thermal conditions.