Polymer thin films operable under concurrent electric and thermal extremes represent critical building blocks of capacitive energy storage and electrical isolator for modern power and electronic systems with ever-increasing demands for power density and payload efficiency. However, polymer dielectrics are prone to fast aging under high fields due to hot electrons injected from electrodes. Especially, performance high-heat polymers such as polyimides with high aromaticity suffer fast aging induced by non-thermalized electrons even at moderate fields due to their intrinsically low bandgap and injection barrier. Herein, a facile, low-cost, and scalable interface-engineering approach utilizing the highly ordered organic/inorganic layered nanocoatings is reported, which serve as a retrofittable solution to break this design constraint. By probing the energetic modes of transport and aging at pre-breakdown field, we demonstrate that our 2D montmorillonite (MMT) self-co-assembly nanocoatings can effectively boost the dielectric properties of substrate polyimide (PI) film by suppressing the charge injection and shifting the fast mode of hot-electron aging to a slow, ultimately thermalized process. This aging-impeding scheme imparts PI films with an exceptional endurance capability (enhanced by 100 MV/m) and a 6× improved charge-discharge efficiency at an elevated temperature of 175 °C. The nanostructured interface engineering disclosed in this work thus opens a new pathway of boosting the performance of a spectrum of high-heat polymer dielectrics already commercially available in thin gauges of films for applications in zero-emission electric aircraft and renewable energy integration.