Solvation of lithium ions in mixed organic electrolyte solutions for secondary lithium batteries was investigated by electrospray ionization mass spectroscopy. The electrolyte solutions were mixed binary solutions of diethyl carbonate (DEC), dimethyl carbonate (DMC), ethylene carbonate (EC),γ-butyrolactone (GBL), and propylene carbonate (PC) containing LiClO4. Lithium ions solvated mainly to two solvent molecules. The order of the inclination of the solvent molecules solvating to lithium ions is PC > EC ≒ GBL >> DEC > DMC