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Electrospun porous nanofibers have gained a lot of interest recently in various fields because of their adjustable porous structure, high specific surface area, and large number of active sites, which can further enhance the performance of materials. This paper provides an overview of the common polymers, preparation, and applications of electrospun porous nanofibers. Firstly, the polymers commonly used to construct porous structures and the main pore-forming methods in porous nanofibers by electrospinning, namely the template method and phase separation method, are introduced. Secondly, recent applications of electrospun porous nanofibers in air purification, water treatment, energy storage, biomedicine, food packaging, sensor, sound and wave absorption, flame retardant, and heat insulation are reviewed. Finally, the challenges and possible research directions for the future study of electrospun porous nanofibers are discussed.