The development of smart negative electrode materials with high capacitance for the uses in supercapacitors remains challenging. Although several types of electrode materials with high capacitance in energy storage have been reported, carbon-based materials are the most reliable electrodes due to their high conductivity, high power density, and excellent stability. The most common complaint about general carbon materials is that these electrode materials can hardly ever be used as free-standing electrodes. Free-standing carbon-based electrodes are in high demand and are a passionate topic of energy storage research. Electrospun nanofibers are a potential candidate to fill this gap. However, the as-spun carbon nanofibers (ECNFs) have low capacitance and low energy density on their own. To overcome the limitations of pure CNFs, increasing surface area, heteroatom doping and metal doping have been chosen. In this review, we introduce the negative electrode materials that have been developed so far. Moreover, this review focuses on the advances of electrospun nanofiber-based negative electrode materials and their limitations. We put forth a future perspective on how these limitations can be overcome to meet the demands of next-generation smart devices.