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We report a new sodium‐ion battery formed by coupling a NaFePO₄ cathode and a nanocomposite tin–carbon (Sn–C) sodium‐alloying anode. The NaFePO₄ cathode is obtained by Li–Na conversion of a LiFePO₄ cathode directly in the full cell employing the Sn–C anode and a sodium‐ion electrolyte. The results show that the unique approach adopted here is capable of successfully and efficiently converting LiFePO₄ into NaFePO₄ in a sodium‐ion battery operating at a voltage of 3 V, with a maximum reversible capacity of 150 mAh g⁻¹, high reversibility, and high rate capability.