The demand for energy storage systems is rising due to the rapid development of electric transportation vehicles, and this demand is stimulating research on the next generation of high-performance, high-density energy storage devices. In this work, nanomaterials with excellent electrochemical properties are of particular significance. This review summarizes a variety of methods based on electrospinning techniques for the preparation of porous nanofibers with controllable morphologies. An emphasis is placed on methods involving polymer templates and polymer blend templates, hard templates, and on solvent-induced, nonsolvent-induced or activation methods. As a simple and cost-effective method for preparing one-dimensional nanomaterials, the electrospinning technique is of special significance in the energy storage field, because the as-prepared porous nanofibers exhibit large specific surface areas and interconnected micro-/meso-/macroporous structures. Both of these features enable greater energy storage. Furthermore, this review presents several suggestions for meeting the challenges involved in the preparation and industrial application of electrospun porous nanofibers for advanced energy storage systems.