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Electrospinning as one of the most versatile technologies have attracted a lot of scientists’ interests in past decades due to its great diversity of fabricating nanofibers featuring high aspect ratio, large specific surface area, flexibility, structural abundance, and surface functionality. Remarkable progress has been made in terms of the versatile structures of electrospun fibers and great functionalities to enable a broad spectrum of applications. In this article, the electrospun fibers with different structures and their applications are reviewed. First, several kinds of electrospun fibers with different structures are presented. Then the applications of various structural electrospun fibers in different fields, including catalysis, drug release, batteries, and supercapacitors, are reviewed. Finally, the application prospect and main challenges of electrospun fibers are discussed. We hope that this review will provide readers with a comprehensive understanding of the structural design and applications of electrospun fibers in different fields.

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