Abstract Polyimide (PI) has excellent resistance to high or low temperatures due to its unique molecular structure, and is widely used in advanced electronics and power systems in extreme environments. In recent years, a small amount of studies have been published to modulate the dynamic behavior of PI such as self‐healable, recyclable, and degradable abilities by adjusting the structure of molecular chains and the composition of monomers. However, the conceptual design, formation conditions, and application prospects of dynamic PI are still unclear. In this paper, the new concepts and systems of dynamic PI are introduced from the perspective of the design of molecular structure, the development of regulating performance area, and the application of extreme insulation, based on recent work and other representative work. Specifically, this work appeals to researchers involved in PI synthesis, smart, dielectric, energy storage, and extreme insulation.