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.