Thermal management plays a vital role in technology (electronic and electrical equipment) and life (high-temperature injury). Therefore, thermal regulation has attracted worldwide attention. This review addresses the applications of electrospinning (e-spinning) in the thermal management of polymer matrix composites, mainly involving enhanced thermal conductivity (TC), thermal insulation, and passive daytime radiative cooling (PDRC). In particular, in the regulation of TC, e-spinning can uniformly distribute active fillers in the composites to achieve bidirectional control. The types of active filler and its connection forms in the composites are discussed emphatically. In addition, PDRC without energy consumption is also highlighted. Finally, the current challenges and future development are addressed.