In order to improve the wettability and electrochemical activity of electrospun carbon nanofibers, the partially reduced graphene oxide doped electrospun carbon nanofibers have been successfully prepared by introducing graphene oxide into the electrospinning solution with a simple electrospinning and subsequent carbonization process. It is found that some of the partially reduced graphene oxide nanosheets with plenty of wrinkles are embedded between the nanofibers, which directly enhances the physical surface area. Despite the introduced graphene oxide is partially reduced during the carbonization process, the corresponding oxygen content is greatly increased, which results in the improved wettability and further a significant enhancement in the electrochemical surface area. It is worth noting that the electrocatalytic activity is almost unchanged, indicating the improved electrochemical response is attributed to the enhanced electrochemical surface area. Moreover, vanadium flow battery with such composites presents a remarkable improvement in the electrochemical performances such as energy efficiency and discharge capacity, further suggesting that such composites are promising high-efficient electrode materials for vanadium flow battery. Therefore, it is believed that the construction of carbon-based electrode with high electrochemical surface area through the anchoring effect of hydrophilic materials is an effective approach to obtain high-efficient electrode materials for vanadium flow battery.