Heat insulation materials are materials that have the ability to insulate heat and impede the transfer of heat flow and are usually characterized by light weight, looseness, high porosity, and low thermal conductivity. Therefore, they are widely used in industries such as thermal equipment and pipeline, construction, aerospace, and other fields. Electrospun nanofibers possess a high specific surface area and controllable pore structure and are often used as heat insulation materials. Furthermore, aerogel refers to a gel composed of microporous solids in which the gas is the dispersed phase and the nanofiber aerogel can be synthesized from nanofibrous membranes. More importantly, the high specific surface area and high thermal stability of nanofibers make the prepared ceramic aerogels more stable at high temperatures. In this chapter, the heat insulation mechanism and conductivity of high-temperature heat insulation materials are described. The high-temperature insulation material is mainly divided into two-dimensional (2D) nanofibrous membrane and 3D nanofiber-based aerogel according to the structure. The research status of 2D electrospun nanofibrous membrane, 3D electrospun nanofiber-based aerogel insulation materials, and application of electrospun nanofiber-based insulation materials is emphatically introduced, and the development of high-temperature insulation materials is prospected.