The properties and abundance of carbon in its different forms resulted in the wide use of carbon-based materials by diverse sectors of industry, science, and technology. Consequently, emerging and anticipated technological challenges have increased the pressure on researchers to develop advanced carbon-based materials. In addition, there will always be a need to search for alternative sources of carbon as well as innovative ways of using available carbonaceous materials for different applications. To date, materials at the nanoscale have emerged as having the greatest potential of addressing existing and emerging materials science challenges. Needless to say, a better understanding of the fabrication and use of carbon-based materials at the nanoscale level via such approach as electrospinning (ES) has become of paramount importance. Since the last decade, ES of polymeric precursors, such as polyacrylonitrile, has been routinely used as a simple and low-cost method to make continuous nanofibers. The chapter discusses the fabrication and properties of electrospun carbon nanofibers, which have been demonstrated to be useful for several applications ranging from energy storage and conversion, biomedical, and adsorption and separation devices due to their superior physicochemical, electrochemical, and mechanical properties.