The aim of this work is to develop a sodium/electrospun poly(5-cyanoindole) nanofiber secondary battery system with the similar performance of lithium ions battery. The experimental cell is assembled using sodium foil as anode, electrospun poly(5-cyanoindole) nanofiber as cathode and NaPF6 containing organic electrolyte solutions. The electrical performance of the sodium/electrospun poly(5-cyanoindole) nanofiber secondary battery system is evaluated by charge/discharge test, rate performance, cycle stability and electrochemical impedance. The results indicate that the sodium/electrospun poly(5-cyanoindole) nanofiber cell has advantages in fast charge/discharge as well as cycle life. It would be a promising system for a less expensive battery with performance approaching that of lithium ions battery.