Xuxuan Pan, Zhuo Wang, Wenhao Zhou, F. Liu, Jun Chen
High-voltage equipment imposes increasingly stringent demands on polymeric insulating materials, particularly in terms of dielectric strength, space charge suppression, thermo-electrical stability, and interfacial reliability. Conventional polymers are prone to critical failure modes under high electric fields, including electrical treeing, partial discharge, interfacial degradation, and thermo-oxidative aging. This review systematically summarizes recent advances in polymer modification strategies specifically designed for high-voltage applications, covering nanofiller reinforcement, plasma surface engineering, and the development of self-healing insulating polymers. Multi-scale structural control and interface engineering, aligned with the specific requirements of high-voltage environments, have emerged as pivotal approaches to enhance insulation performance. Moreover, the integration of artificial intelligence-driven materials design, digital characterization, and application-oriented modeling holds significant promise for accelerating the development of next-generation high-voltage polymeric systems, thereby offering robust materials solutions for the reliable long-term operation of high-voltage equipment.