New functionalized ILs based on quaternary ammonium cations with two ether groups and bis(trifluoromethanesulfonyl)imide (TFSA−) anion are synthesized and characterized. Physical and electrochemical properties, including melting point, thermal stability, viscosity, conductivity and electrochemical stability are investigated for these ILs. All these ILs are liquids at room temperature except N,N-diethyl-N,N-bis(2-ethoxyethyl)ammonium TFSA (N22(2o2)(2o2)-TFSA, T m = 29.7 °C), and the viscosities of N-methyl-N-ethyl-N-(2-methoxyethyl)-N-(2-ethoxyethyl)ammonium TFSA (N12(2o1)(2o2)-TFSA) and N-methyl-N-ethyl-N,N-bis(2-ethoxyethyl)ammonium TFSA (N12(2o2)(2o2)-TFSA) are 68.0 cP and 63.0 cP at 25 °C, respectively. N-Methyl-N,N-diethyl-N-(2-methoxyethyl)ammonium TFSA (DEME–TFSA) and five ILs with lower viscosity are chosen to dissolve 0.6 mol kg−1 of LiTFSA as IL electrolytes without additive for lithium battery. Lithium plating and striping on Ni electrode can be observed in these IL electrolytes, and cycle performances of lithium symmetrical cells are also investigated for these IL electrolytes. Li/LiFePO4 cells using these IL electrolytes without additives have good cycle property at the current rate of 0.1 C, and the N-methyl-N-ethyl-N,N-bis(2-methoxyethyl)ammonium TFSA (N12(2o1)(2o1)-TFSA) and N12(2o2)(2o2)-TFSA electrolytes own better rate property than DEME–TFSA electrolyte.