Abstract: With the continuous development of electronic equipment towards miniaturization, integration and multifunction, the high thermal conductivity of electronic materials has become critically significant to ensure the stable operation and service life of electronic equipment. Polyimide (PI) is widely used in the thermal management field because of its excellent heat resistance and mechanical properties. However, the intrinsic thermal conductivity of traditional PI is low, which is difficult to meet the rapid heat dissipation requirements of electronic devices. The development of new highly thermally conductive PI and PI composites has become a research hotspot. This paper introduces the preparation and performance regulation of amorphous polyimides and liquid crystalline polyimides based on the molecular chain structure, molecular chain orientation and molecular interaction of intrinsic thermally conductive PI, and discusses the influence of surface modification, constructing hybrid fillers, orientation design, three-dimensional network structure on the structure and performance of PI composites. Finally, the challenges of highly thermally conductive PI and PI composites are summarized and prospected.