The greater availability of sodium with large storage capacity motivates the fabrication of advanced electrodes materials for sodium ion batteries (SIBs) to promote in potential market of smart appliances. Multiple metals atomic dispersion into carbon framework can enhance the adsorption property of sodium for high performance SIBs. In this work, rationalized atomic/clusters of Fe/Se/Al are dispersed on N-doped amorphous carbon fibers through electrospinning and direct selenization (DS) processes. The developed product of DS-Fe/Se/Al@NC-650 nanofibers are employed as anode materials of SIBs, exhibitinga high specific capacity of 432 mAh g−1 at 100 mA g−1 a desirable cycling stability with a capacity retention of 99 % after 700 cycles. Such an excellent storage capacity initiates through synergistic effects of the uniformly distributed Fe/Se/Al and the interconnected nitrogen-doped carbon network. For the apprehension of capacity and stability of DS-Fe/Se/Al@NC-650 nanofibers for SIBs, the theoretical calculations were carried out and provide strong evidences which proves the electron/ion transport in experimental results.