Electrospinning is a useful and convenient method for producing ultrathin fibers. It has grabbed the scientific community’s interest due to its potential to produce fibers with various morphologies. Numerous efforts have been made by researchers and industrialists to improve the electrospinning setup and the associated techniques in order to regulate the morphology of the electrospun fibers for practical applications. Porous, hollow, helical, aligned, multilayer, core-shell, and multichannel fibers have been fabricated for different applications. This chapter aims to provide readers with a clear understanding of the electrospinning process: its principle, methodology, materials, and applications. The chapter begins with a brief introduction to the history of electrospinning, followed by a discussion of its principle and the basic components of electrospinning setup. The parameters that affect the electrospinning process such as operating parameters and the properties of the material being electrospun are discussed briefly. An overview of the different types of electrospinning technique, capable of producing nanofibers with different morphologies, is also presented. Afterward, the applications of electrospun nanofibers, including their use in biomedical applications, filtration, energy sectors, and sensors applications are discussed succinctly. The perspectives on the challenges, opportunities, and new directions for future development of electrospinning technology are also offered.