This review is based on the fundamental aspects and applications of polyacrylonitrile (PAN)‐based electrospun composite nanofibers. Various electrospinning techniques have been discussed here. polyacrylonitrile is an acrylic polymer of commercial significance that has superior thermal, mechanical, electrical, and chemical properties. The integration of polyacrylonitrile nanofibers with nanoparticles including carbon nanotubes, graphene nanosheets, graphene oxide, metal oxides, and their combinations has greatly improved the physicochemical properties of the polyacrylonitrile electrospun nanofibers. The enhanced features of polyacrylonitrile nanofibers have resulted from interfacial bonding of nitrile groups with the nanofiller used, chemical compositions, hydrophobicity, porosity, and wettability of these nanofibers. This article fundamentally features a few key possibilities of polyacrylonitrile‐based electrospun composite nanofibers and their applications. A special focus has been made on polyacrylonitrile‐based inorganic nanoparticles, graphene nanosheets, graphene oxide, and carbon nanotubes embedded electrospun nanofibers, for their potential applications in supercapacitors, high power batteries, filtration membranes, electromagnetic interference shielding, and strain sensors. Achieving low cost, high selectivity, excellent recyclability, and high absorption capability are the major challenges for electrospun nanofiber fabrications. These electrospun nanofibers require extensive research in the future to advance the technologies to bring them to the commercial market.

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