A solid state Na+ electrolyte is developed by dissolving Na+ salts into the organic crystal succinonitrile, which exhibits a high ionic conductivity of ∼10−3 Scm−1 at room temperature and a wide electrochemical window of >3V. Based on this solid-state electrolyte, an all-organic Na–ion battery is constructed by use of poly(aniline/o-nitroaniline) (P(AN-NA)) cathode and poly(anthraquinonyl sulfide) (PAQS) anode. This solid-state battery works well with an open circuit voltage of 2.4V and can be cycled at considerable high rate of >800mAg−1, showing a competitive performance to the organic solvent Na-ion batteries.