Carbon nanofibers with multi-scale pores have been easily constructed by synchronous water etching during the carbonization process of PAN nanofibers, reducing the additional consumption of energy and time. After etching by high-temperature water vapor, the fiber surface becomes more coarse, and large amounts of etched pits are formed, effectively increasing the electrode’s specific surface area and hydrophilicity. Oxygen content is also significantly increased, which may effectively increase the electrocatalytic active sites of the electrode. Electrochemical tests verified the improved electrocatalytic activity and increased effective surface area. As a result, the VRFB single cell with water vapor etched carbon nanofibers as its electrode shows higher battery efficiencies than that with pristine carbon nanofibers; the energy efficiency improves by nearly 9.4% at 200 mA·cm-2. After 100 charge/discharge cycles, the battery efficiency has no obvious attenuation, and the capacity attenuation rate of single cycle is nearly 0.26%,suggesting a satisfactory cycling stability. This green and simple method for constructing multi-scale porous carbon nanofibers electrode is expected to achieve large-scale production of high-performance electrode materials, and can be applied in various electrochemical energy storage systems.