The high efficient energy storage, lithium-ion batteries (LIBs) is accounted as one of the most important storage devices to facilitate the transition of renewable energy conversion. The electrolyte component is the most important in deciding the capacity of LIBs. Lithium bis(fluorosulfonyl)imide (LiFSI) is recently considered as promising conducting electrolyte salt for LIBs because it shows enabling high voltage, high energy density, long cycle life, and accelerates the fast-charging Li-ion batteries. Generally, Additionally, LiFSI and LiPF₆ based electrolyte are used in the most of commercial LIBs. Last few years, LiFSI is regarded as an alternative electrolyte to the classical LiFP₆ due to its high ionic conductivity, good thermal stability, and HF free nature. In this work, the controlled mixing of ionic liquids (ILs) (imidazolium salts and pyridinium salts) in LiFSI electrolyte was carried out to enhance the ionic conductivity, thermal stability, viscosity, and solubility in organic solvents. The ILs modified LiFSI electrolyte was prepared by adding a constant 1.0 M LiFSI and varying the concentration of ILs from 5 to 20% volume in trimethyl phosphate (TMP). After the modification by ILs, the ionic conductivity of LiFSI electrolyte (10.623 mS/cm) was considerably increased as compared to LiFSI only. The flammability test of electrolyte revealed that ILs modified LiFSI electrolyte was non-flammable, indicating excellent stability in any circumstances. The prepared ILs modified LiFSI electrolyte was used to fabricate coin cell LIBs using double-coated side electrodes (both CMS graphite/Li-NCM (5:2:3) and CMS graphite/LiFePO₄). From GCD analysis, the fabricated LIBs with ILs modified LiFSI electrolyte showed a significant improvement in the charging/discharging ability as compared to commercial LIBs with LiPF₆ electrolyte. This study manifests that the modification of LiFSI by novel ILs would be promising to achieve highly efficient liquid electrolytes for high performance LIBs.