Electrospun porous carbon nanofiber mats have excellent properties, such as a large surface area, tunable porosity, and excellent electrical conductivity, and have attracted great attention in energy storage and power generation applications. Moreover, due to their exceptional properties, they can be used in dye-sensitized solar cells (DSSCs), membrane electrodes for fuel cells, catalytic applications such as oxygen reduction reactions (ORRs), hydrogen evolution reactions (HERs), and oxygen evolution reactions (OERs), and sensing applications such as biosensors, electrochemical sensors, and chemical sensors, providing a comprehensive insight into energy storage development and applications. This study focuses on the role of electrospun porous carbon nanofiber mats in improving energy storage and generation and contributes to a better understanding of the fabrication process of electrospun porous carbon nanofiber mats. In addition, a comprehensive review of various alternative preparation methods covering a wide range from natural polymers to synthetic carbon-rich materials is provided, along with insights into the current literature.