Tetraglyme (G4)–lithium bis(trifluoromethanesulfonyl)amide (TFSA) complexes with different G4 ratio were investigated. An increase in the amount of G4 led to the decrease in the viscosity, and increase in the ionic conductivity of the complex, and G4–LiTFSA showed higher thermal stabilities than the conventional organic electrolyte, when the molar ratio of G4 was more than 40mol%. The increase in the G4 amount improved the rate capabilities of Li/LiCoO2 cells in the range where the molar ratio of G4 was between 40mol% and 60mol%. The stable Li ion intercalation–deintercalation was not observed in the Li/graphite cell of [Li(G4)][TFSA] (G4: 50mol%) without additives. However, the additives for forming solid electrolyte interface (SEI) film, such as vinylene carbonate, vinylethylene carbonate, and 1,3-propane sultone, led to the charge–discharge performance comparable to that of the conventional organic electrolyte. The adoption of Li4Ti5O12 and LiFePO4 led to excellent reversibilities of the Li half cells using [Li(G4)][TFSA], probably because of the favorable operation voltage. In the case of the LiFePO4/Li4Ti5O12 cell, the cell with [Li(G4)][TFSA] showed the better rate capability than that with the conventional organic electrolyte, when the rate was less than 1 CmA, and it is concluded that [Li(G4)][TFSA] can be the candidate as the alternative of organic electrolytes when the most appropriate electrode-active materials are used.