Butylmethylpyrrolidinium bis(trifluoromethanesulfonyl)imide (BMP–TFSI) ionic liquid (IL) with LiTFSI solute is used as a base electrolyte for Li/LiFePO4 cells. Three kinds of electrolyte additive, namely vinylene carbonate (VC), gamma-butyrolactone (γ-BL), and propylene carbonate (PC), with various concentrations are introduced. The thermal stability, flammability, and electrochemical properties of the electrolytes are investigated. At 25 °C, the additives (γ-BL is found to be the most effective) can significantly improve the capacity, high-rate performance, and cyclability of the cells. With an increase in temperature to 50 °C, the benefits of the additives gradually become insignificant. At 75 °C, the additives even have adverse effects. At such an elevated temperature, in the plain IL electrolyte (without additives), a LiFePO4 capacity of 152 mAh g−1 is found at 0.1 C. 77% of this capacity can be retained when the rate is increased to 3 C. These values are superior to those found for the additive-incorporated IL and conventional organic electrolytes. Moreover, negligible capacity loss is measured after 100 charge–discharge cycles at 75 °C in the plain IL electrolyte.