Many electrochemical energy storage and conversion devices employ porous media as electrodes, gas diffusion layers or separators. Recently, electrospinning has received significant attention as a way to generate nano‐fibers of polymers with controlled morphology and properties that, once carbonised, can act as conductive and porous media for electrochemical energy devices. The recent advances in X‐ray computed tomography have led the technique to be widely used in the characterisation of energy technologies and porous media as it offers a uniquely non‐destructive insight into the 3D microstructure of materials. Here we present electrospun fibrous mats with uncontrolled, controlled and aligned morphology for use as redox flow battery electrodes and, for the first time, obtain ultra‐high resolution nano‐tomographic X‐ray imaging of the materials using a lab source. The virtual 3D volumes enable extraction of parameters that would not be possible via other characterisation routes.