Dielectric capacitors play a pivotal role in advanced high-power electrical and electronic applications, acting as essential components for electrical energy storage. The current trend towards miniaturization in electronic devices and power systems highlights the increasing demand for scalable, high-performance ultra-thin dielectric films with a high-temperature stability. While significant progress has been made in enhancing the discharged energy density (Ue) of dielectric polymers at elevated temperatures, such advancements have faced certain challenges. Herein, an innovative molecular engineering approach for the bonding of amine-functionalized molybdenum trioxide (A-MoO3) with the dianhydride monomer of polyetherimide (PEI) is presented, leading to a reduction in conduction loss and the substantial enhancement in storage energy density under high-temperature and high-field conditions. It is revealed that charge redistribution at the bonding sites induces a subtle variation in the potential energy, creating an in-built electric field between the PEI matrix and A-MoO3 based on density functional theory (DFT) analyses. The observed phenomenon leads to an increase in the electron barrier, effectively inhibiting the release of trapped electrons. Notably, at conditions of 200 °C and 100 Hz, the PEI/A-MoO3 hybrid film demonstrates a notable Ue at η > 90%, reaching up to 5.53 J cm-3, surpassing the performance of many current dielectric polymers and composites. Furthermore, the hybrid film's exceptional cycling durability, coupled with its ability to be fabricated into large-area, uniform-quality films, underscores its potential in the development of dielectric energy storage devices tailored for extreme environments.