Radioactive aerosols are highly hazardous aerosols containing radionuclides. Inhalation of radioactive aerosols can lead to serious internal exposure hazards to human body. If discharged without proper treatment, it will also harm the working environment and even the ecological environment. Therefore, radioactive aerosol protection is a significant part of environmental protection and personnel protection in the nuclear field. However, majority of existing protective fabrics for radioactive aerosol filtration always meet the trade-off among filtration capacity, mechanical properties and air permeability. In this study, nanofiber layers were prepared by electrospinning technology using TPU, PVDF, PVA polymer materials and electret materials SiO2 as spinning materials. Composite membranes, prepared by coating different nanofiber layers on the PET non-woven fabrics substrate, were investigated. The results show that the 12wt% TPU nanofiber membrane has a three-dimensional spatial hierarchical structure. Its ultra-fine fiber diameter with small pore size greatly enhances the PM capture ability (PM0.3 filtration efficiency 99.99%); and the beaded spatial structure is beneficial to reduce the air resistance to 299 Pa (flow rate 95 L/min). Meanwhile, TPU nanofiber membrane has high extensibility, and it is superior to PVDF and PVA composite membranes in mechanical properties after thermal compounding. Appropriate content of SiO2 can improve filtration performance. The study shed light on developing electrospun nanofiber for radioactive aerosol protection, which can be used in the purification of ambient air in nuclear facilities, or as a high-performance fabric for radioactive aerosol protective clothing.