Na[FSA–C2C1im][FSA] (C2C1im+:1-ethyl-3-methylimidazolium and FSA−:bis(fluorosulfony)amide) ionic liquid was utilized as the aprotic electrolyte in hybrid sodium–air cells for the first time. The sodium–air cells were operated at relatively high temperatures up to 70°C to prove their excellent thermal stability. A large output power density was obtained by increasing the operation temperature because of the high Na+ diffusivity and high ionic conductivity of the ionic liquid. The cells exhibited an extremely large specific capacity of 835mAhg−1 at 50°C; this capacity corresponds to 99% of the theoretical capacity. In addition, maximum areal output power density of 27.6mWcm−2 was obtained at 50°C. The Na[FSA–C2C1im][FSA] ionic liquid was proved to be a promising aprotic electrolyte to enhance the electrochemical performance of hybrid sodium–air cells.