Abstract: Under the severe challenges brought by intensifying global energy consumption and warming, radiative cooling, as a passive cooling technology that requires no external energy input, shows great potential by efficiently dissipating an object's own heat to the cold outer space in the form of infrared radiation. Applying this principle to daily wearable textile fibrous materials to achieve personal cooling and improve thermal comfort has become a very promising research direction. Electrospinning technology has become an effective preparation method for constructing high-performance radiative cooling fibrous materials, due to its unique advantage of being able to prepare nanofibers with high specific surface area, high porosity, and controllable micro-nano structures. This review focuses on the latest research progress using electrospinning technology to prepare radiative cooling fibrous materials. First, it briefly describes the basic principles of radiative cooling and discusses how the unique structure that electrospinning imparts to nanofibers can allow them to effectively regulate the material's infrared optical properties. On this basis, the research progress in the design, preparation and properties of polymers and polymer/functional filler composites based on electrospinning was systematically combed. Furthermore, based on practical application needs, the research progress of electrospun radiative cooling fiber materials in multifunctional aspects such as UV protection, controllable coloration, self-cleaning, and dynamic radiation regulation is discussed. Meanwhile, relevant research on the large-scale preparation of radiative cooling fibrous materials is also explored. Finally, the current challenges faced in the field of material performance optimization and practical applications are analyzed, and future development directions are prospected, aiming to provide references for promoting the research, development, and application of advanced electrospun radiative cooling fiber materials.