Sodium rechargeable batteries can be excellent alternatives to replace lithium rechargeable ones because of the high abundance and low cost of sodium; however, there is a need to further improve the battery performance, cost-effectiveness, and safety for practical use. Here we demonstrate a new type of room-temperature and high-energy density sodium rechargeable battery using an SO2-based inorganic molten complex catholyte, which showed a discharge capacity of 153 mAh g(-1) based on the mass of catholyte and carbon electrode with an operating voltage of 3 V, good rate capability and excellent cycle performance over 300 cycles. In particular, non-flammability and intrinsic self-regeneration mechanism of the inorganic liquid electrolyte presented here can accelerate the realization of commercialized Na rechargeable battery system with outstanding reliability. Given that high performance and unique properties of Na-SO2 rechargeable battery, it can be another promising candidate for next generation energy storage system.