Vanadium redox flow batteries (VRFBs) are considered as promising electrochemical energy storage systems due to their efficiency, flexibility and scalability to meet our needs in renewable energy applications. Unfortunately, the low electrochemical performance of the available carbon-based electrodes hinders their commercial viability. Herein, novel free-standing electrospun nanofibrous carbon-loaded composites with textile-like characteristics have been constructed and employed as efficient electrodes for VRFBs. In this work, polyacrylonitrile-based electrospun nanofibers loaded with different types of carbon black (CB) were electrospun providing a robust free-standing network. Incorporation of CBs (14% and 50% weight ratio) resulted in fibers with rough surface and increased mean diameter. It provided higher BET surface area of 83.8 m 2 g −1 for as-spun and 356.7 m 2 g −1 for carbonized fibers compared to the commercial carbon felt (0.6 m 2 g −1). These loaded CB-fibers also had better thermal stability and showed higher electrochemical activity for VRFBs than a commercial felt electrode. The need for modern and effective grid-connected energy storage systems is growing worldwide due to the expansion of only intermittently available renewable energy sources and the inherent request for services of power quality and energy management. Redox flow batteries (RFBs), especially all-vanadium RFBs (VRFBs), have been considered as promising stationary electrochemical storage systems to compensate and stabilize the power grid. This is attributed to their unique features such as their flexibility, scalability, independently scaled power and energy, high efficiency, room temperature operation, and extremely long charge/discharge cycle life 1-3. The electrodes are the essential components of the VRFBs since their morphological, structural, chemical and physical properties affect the overall improved performance, durability, efficiency and even the total cost of the VRFBs technology 4. Currently, the most commonly used materials for electrodes are carbon-based materials including carbon cloth, carbon-polymer composite, graphite felt, carbon paper and graphene 5 thanks to their low cost, safety, stability and their inertness. However, their relatively low electrochemical activity towards the vanadium redox reactions together with their poor wettability limit the battery power density. In this perspective, several strategies have been introduced to overcome the mentioned issues and to improve the carbon-based materials performance. These strategies are mainly based on acid, thermal and (electro-)chemical treatments as well as surface modifications by functionalizing the surface with hetero-atom functional groups (i.e. OH, SH, NH 2) or by surface coating with catalysts such as Bi, Mn, Ir or metal oxides (PbO 2 , CeO 2 , Mn 3 O 4 , ZrO 2 , Ce 0.8 Zr 0.2 O 2 , Nd 2 O 3 , etc.) 6-13. For instance, surface modification by boiling in concentrated sulphuric acid for 5 h led to a dramatic improvement in the electrocatalytic activity ...