Aerogels are gels in which the solvent is supplanted by air while the pores and networks are largely maintained. Owing to their low bulk density, high porosity, and large specific surface area (SSA), aerogels are promising for many applications. Various inorganic aerogels, e.g., silica aerogels, are intensively studied. However, the mechanical brittleness of common inorganic aerogels has seriously restricted their applications. In the past decade, nanofibers have been developed as building blocks for the construction of aerogels to improve their mechanical property. Unlike traditional frameworks constructed by interconnected particles, nanofibers can form chemically cross-linked and/or physically entangled 3D skeletons, thus showing flexibility instead of brittleness. Therefore, excellent elasticity and toughness, ultralow density, high SSA, and tunable chemical composition can be expected for the polymer nanofiber-derived aerogels (PNAs). In this review, recent research progress in the fabrication, properties, and applications of PNAs is summarized. Various nanofibers, including nanocelluloses, nanochitins, and electrospun nanofibers are included, as well as carbon nanofibers from the corresponding organic precursors. Typical applications in supercapacitors, electrocatalysts for oxygen reduction reaction, flexible electrodes, oil absorbents, adsorbents, tissue engineering, stimuli-responsive materials, and catalyst carriers, are presented. Finally, the challenges and future development of PNAs are discussed.