Although electrospun carbon nanofibers (ECNFs) possess excellent conductivity, high surface area and good electrochemical activity toward vanadium redox couples, much surface area of ECNFs was still unutilized because of its poor hydrophilicity. CeO2 nanoparticles as an excellent hydrophilic agent are embedded in polyacrylonitrile (PAN) based carbon nanofibers by a simple electrospinning and subsequent carbonization process. The physicochemical characterizations show that the introduction of CeO2 nanoparticles slightly changes the structure and compositions of ECNFs, while the corresponding wettability is greatly improved. It is worth noting that the electrochemical surface area (ECSA) of CeO2/ECNFs is more than four times of that for ECNFs. According to the cyclic voltammograms (CV) and electrochemical impedance spectra (EIS) results, the addition of CeO2 improves the electrocatalytic activity toward the negative reaction of vanadium flow battery (VFB) to some extent while has less effect on that toward the positive reaction, the significant improvement in the electrochemical performance of CeO2/ECNFs might be mostly ascribed to the remarkable enhancement in ECSA. In addition, the charge/discharge tests further verify that CeO2/ECNFs with high ECSA could significantly reduces the electrochemical polarization during the discharging process and results in an enhanced discharge capacity and energy efficiency. The accomplishment of this work provides a new concept that it might be more convenient and effective to improve the electrochemical performance of the electrode materials for VFB by increasing their ECSA.