Polymer dielectrics with high operation temperature (∼150 °C) and excellent capacitive energy storage performance are vital for electric power systems and advanced electronic devices. Here, a very convenient and competitive strategy by preparing ultraviolet-irradiated cyclic olefin copolymer films is demonstrated to be effective in improving the energy storage performance at high temperatures. Compared with the unirradiated film, irradiated films exhibit a higher dielectric constant, higher breakdown strength and stronger mechanical properties as a result of the emergence of the carbonyl group and cross-linking network. Consequently, with a high efficiency above 95%, a superior discharged energy density of ∼3.34 J cm-3 is achieved at 150 °C, surpassing the current dielectric polymers and polymer nanocomposites. In particular, the energy storage performance remains highly reliable over 20 000 cycles under actual operating conditions (200 MV m-1 at 150 °C) in hybrid electric vehicles. This research offers a valuable pathway to build high-energy-density polymer-based capacitor devices working under harsh environments.