This study aims to develop an aqueous zinc/electrospun poly(5-cyanoindole) fibers secondary battery system. Zn foil and ZnCl2 are used as anode active materials and the electrolytic solution, respectively. Poly(5-cyanoindole) synthesized by chemical oxidation is electrospun into fibers and used as cathode active materials. FTIR and NMR test are carried out to investigate the chemical structure of poly(5-cyanoindole). Surface properties of electrospun poly(5-cyanoindole) fibers are studied by SEM, TEM, and BET. The performance of zinc/electrospun poly(5-cyanoindole) fibers battery system is evaluated in term of electrical conductivity, cyclic voltammogram, electrochemical impedance spectroscopy, discharge capacity and durability test. The cell achieves 2.0 V electromotive force with about 107–61 Ah Kg−1 discharge capacity at 0.2C–10C rate. At 800th cycle, the discharge capacity remains 80–57 Ah Kg−1 at 0.2C–2C rate, which is about 75–63% of the maximum discharge capacity. These results indicate that the cell has very excellent cyclic properties as well as fast charge/discharge properties. Electrospun poly(5-cyanoindole) fibers have been proved to be a better candidate than polyindole powder as cathode material in zinc/polymer battery.