Lithium vanadium fluorophosphate, LiVPO4F, was utilized as both cathode and anode for fabrication of a symmetric lithium-ion LiVPO4F//LiVPO4F cell. The electrochemical evolution of the LiVPO4F//LiVPO4F cell with the commonly used organic electrolyte LiPF6/EC-DMC has shown that this cell works as a secondary battery, but exhibits poor durability at room temperature and absolutely does not work at increased operating temperatures. To improve the performance and safety of this symmetric battery, we substituted a non-flammable ionic liquid (IL) LiBF4/EMIBF4 electrolyte for the organic electrolyte. The symmetric battery using the IL electrolyte was examined galvanostatically at different rates and operating temperatures within the voltage range of 0.01–2.8V. It was demonstrated that the IL-based symmetric cell worked as a secondary battery with a Coulombic efficiency of 77% at 0.1mAcm−2 and 25°C. It was also found that the use of the IL electrolyte instead of the organic one resulted in the general reduction of the first discharge capacity by about 20–25% but provided much more stable behavior and a longer cycle life. Moreover, an increase of the discharge capacity of the IL-based symmetric battery up to 120mAhg−1 was observed when the operating temperature was increased up to 80°C at 0.1mAcm−2. The obtained electrochemical behavior of both symmetric batteries was confirmed by complex-impedance measurements at different temperatures and cycling states. The thermal stability of LiVPO4F with both the IL and organic electrolytes was also examined.