A simple and fast microwave-assisted protocol to functionalize commercially available graphite felts (GFs) with carbon nanofibers (CNFs) for the application as electrode materials in redox-flow batteries (RFB) is demonstrated. As catalyst for the CNF synthesis nickel acetate is applied and ethanol serves as the carbon source. By the in-situ growth of CNFs, the active surface of the electrodes is increased by a factor of 50, which is determined by the electrochemical double layer capacities of the obtained materials. Furthermore, the morphology of the CNF-coating is investigated by scanning electron microscopy. Subsequently, the functionalized electrodes are applied in a polymer-based redox-flow battery (pRFB) using a TEMPO- and a viologen polymer as active materials. Due to the increased surface area as compared to an untreated graphite felt electrode, the current rating is improved by about 45% at 80 mA cm−2 and, furthermore, a decrease in overpotentials is observed. Thus, using this microwave-assisted synthesis approach, CNF-functionalized composite electrodes are prepared with a very simple protocol suitable for real life applications and an improvement of the overall performance of the polymer-based redox-flow battery is demonstrated.