This study focuses on the electrochemical behavior of thin-layer fibrous carbide-derived carbon (CDC) electrospun electrodes in commercial and research and development stage organic-solvent and ionic liquid (IL) based electrolytes. The majority of earlier published works stated various electrolytes with asymmetric cells of powder-based pressure-rolled (PTFE), or slurry-cast electrodes, were significantly different from the presented CDC-based fibrous spun electrodes. The benefits of the fibrous structure are relatively low thickness (20 µm), flexibility and mechanical durability. Thin-layered durable electrode materials are gaining more interest and importance in mechanically more demanding applications such as the space industry and in wearable devices, and need to achieve a targeted balance between mechanical, electrical and electrochemical properties. The existing commercial electrode technologies lack compatibility in such applications due to their limited mechanical properties and high cost. The test results showed that the widest potential window dU ≤ 3.5 V was achieved in 1.5 M 1-ethyl-3-methylimidazoliumbis(trifluoromethyl-sulfonyl)imide (EMIm-TFSI) solution in acetonitrile (ACN). Gravimetric capacitance reached 105.6 F g−1 for the positively charged electrode. Cycle-life results revealed stable material capacitance and resistance over 3000 cycles.