Using sodium, instead of lithium, in rechargeable batteries is a way to circumvent the lithium's resource problem. The challenge is to find an electrode material that can reversibly undergo redox reactions in a sodium-electrolyte at the desired electrochemical potential. We proved that indigo carmine (IC, 5,5′-indigodisulfonic acid sodium salt) can work as a positive-electrode material in not only a lithium-, but also a sodium-electrolyte. The discharge capacity of the IC-electrode was ~100 mAh g−1 with a good cycle stability in either the Na or Li electrolyte, in which the average voltage was 1.8 V vs. Na+/Na and 2.2 V vs. Li+/Li, respectively. Two Na ions per IC are stored in the electrode during the discharge, testifying to the two-electron redox reaction. An X-ray diffraction analysis revealed a layer structure for the IC powder and the DFT calculation suggested the formation of a band-like structure in the crystal.