In response to the application requirements of secondary batteries at low temperature, an all-organic dual-ion battery with calcium perchlorate contained acetonitrile as the electrolyte (CAN-ODIB) is fabricated in this work. The electrochemical energy is stored in CAN-ODIB via the association and disassociation of calcium and perchlorate ions in perylene diimide-ethylene diamine/carbon black composite based anode and polytriphenylamine based cathode with highly reversible redox states. Benefiting from the energy storage mechanism, CAN-ODIB exhibits excellent electrochemical performances in tests with the temperature ranging from 25 to −50 °C. Especially, CAN-ODIB at −50 °C reserves ≈61% of the capacity at 25 °C (83.4 mA h g⁻¹) with the current density of 0.2 A g⁻¹. CAN-ODIB also shows excellent cycling stability at low temperature by retaining 90.3% of the initial capacity at 1.0 A g⁻¹ after 450 charge–discharge cycles at −30 °C. The impedance analysis of CAN-ODIB at different temperatures indicates that the low temperature performance of CAN-ODIB depends more on the electrode materials than the electrolyte, which provides the important guidance for the further design of secondary batteries operable at low temperatures.