Tailoring the surface morphology of nanofibers determines its application to an excessive extent. At present, different structures of nanofibers have been produced such as wrinkled, grooved, porous, rough, etc. Amongst them, wrinkled nanofibers have attracted the attention of researchers due to their exceptional structure and properties such as coarse surface, high surface energy, high specific surface area, excellent mechanical properties, and good piezoelectricity resulting in serving successfully in various fields such as energy harvesting, air filtration, water filtration, gas sensors, biomedical applications, fuel cells, and energy storage. Therefore, this work aims to spotlight the importance of the wrinkled structure, methods, and strategies used for producing electrospun wrinkled nanofibers of various materials. This review focuses on the materials, preparation methods, and applications of the electrospun wrinkled nanofibers. This review can serve as an essential reference for the materials, formation methods, and applications of wrinkled nanofibers prepared via electrospinning.