The thermal stability of some mixed-solvent electrolytes used in lithium cells was measured by differential scanning calorimetry (DSC) using airtight containers. The electrolytes used were ethylene carbonate (EC) + diethyl carbonate (DEC), EC + dimethyl carbonate (DMC), propylene carbonate (PC) + DEC, and PC + DMC in which was dissolved 1 M LiPF6 or 1 M LiClO4. The influence of water addition and lithium metal addition on the thermal behavior of these electrolytes was also investigated. The exothermic peak of LiPF6 electrolytes containing DEC was found at 255 degreesC, and the peak temperature of the electrolytes containing DEC was 15-20 degreesC lower than that of LiPF6 electrolytes containing DMC. This effect was also observed in the electrolytes including LiClO4. DMC was found to be more reactive than DEC. The thermal behavior of various kinds of LiPF6 electrolytes with lithium metal was measured by DSC. The exothermic reaction of 1 M LiPF6/EC + DEC, 1 M LiPF6/EC + DMC, and 1 M LiPF6/PC + DMC with lithium metal began at the melting point of lithium metal because of the break down of the solid electrolyte interface (SEI). The temperature was approximately 180 degreesC, whereas the self-heating of I M LiPF6/PC + DEC occurred before the melting point of lithium metal. The temperature at which the self-exothermal reaction began was 140 degreesC. Therefore, the lithium metal in this electrolyte was found to be thermally unstable. When water was added to the above electrolytes with lithium metal, the exothermic reaction began at less than 130 degreesC. probably due to a collapse of SEI in response to the HF that was a product of the reaction between LiPF6 and the added water.