Current LIBs with flammable electrolytes are suffering from ignition or explosion of the device due to their poor thermal stability. In this regard, ionic liquids (ILs) can be useful candidates for non-flammable electrolytes due to their high decomposition temperature, non-volatility, and high ionic conductivity. Therefore, we synthesized ionic liquids which are based on pyrrolinium cations with high ionic conductivity as well as fire resistance for application to LIBs as electrolytes. The properties of the ILs were studied by nuclear magnetic resonance (NMR), impedance spectroscopy, thermogravimetric analysis (TGA), differential scanning calorimeter (DSC), viscometer and linear sweep voltametry (LSV). Furthermore, we applied synthesized ILs to the half-coin cells with electrolytes. Coin cells with pyrrolinium ILs showed a sufficient cycle life even at over 50 charge/discharge cycles.