Radiative cooling is an approach that maximizes the thermal emission through the atmospheric window in order to dissipate heat, while minimizing the absorption of incoming atmospheric radiation, to realize a net cooling effect without consuming energy. Electrospun membranes are made of ultra-thin fibers with high porosity and surface area, which makes them suitable for radiative cooling applications. Many studies have investigated the use of electrospun membranes for radiative cooling, but a comprehensive review that summarizes the research progress in this area is still lacking. In this review, we first summarize the basic principles of radiative cooling and its significance in achieving sustainable cooling. We then introduce the concept of radiative cooling of electrospun membranes and discuss the selection criteria for materials. Furthermore, we examine recent advancements in the structural design of electrospun membranes for improved cooling performance, including optimization of geometric parameters, incorporation of highly reflective nanoparticles, and designing multilayer structure. Additionally, we discuss dual-mode temperature regulation, which aims to adapt to a wider range of temperature conditions. Finally, we provide perspectives for the development of electrospun membranes for efficient radiative cooling. This review will provide a valuable resource for researchers working in the field of radiative cooling, as well as for engineers and designers interested in commercializing and developing new applications for these materials.