Blue energy (or salinity gradient energy) is a renewable, carbon-neutral, and continuous electrical energy source that can be obtained via the reverse electrodialysis (RED) technique. The viability of this technology strictly depends on the performance and cost of the ion-exchange membranes (IEMs) that compose the RED units; designing the optimal membrane represents a critical challenge due to the complex relation between the performance, properties, and structure of the membrane. In this work, we present our findings on an electrospun cation-exchange membrane based on polyvinyl chloride (PVC), a strongly acidic cation exchange resin, with sodium dodecyl sulfate (SDS) as an additive. We contrast it with a similar membrane produced with the more conventional casting solution technique. The electrospinning technique provides thinner and more homogeneous membranes than those synthesized via casting. The membranes were characterized using morphological, spectroscopic, and analytical methods. Scanning electron microscopy images depicted an intertwined nanofiber mesh within the membrane. We also synthesized the same electrospun cation exchange membrane without SDS; this membrane presented 63% less swelling, and a significant increase in the fixed charge density (CDfix) (119.6 meq/g) when compared to its casting solution counterpart (34 meq/g). This suggests an enhanced permselectivity, and thus better performance for blue energy generation in RED units.