The thermal stability of lithium-ion battery electrolyte could substantially affect the safety of lithium-ion battery. In order to disclose the thermal stability of 1.0 mol·L-1 LiPF6/ethylene carbonate (EC)+dimethyl carbonate (DMC)+ethylmethyl carbonate (EMC) electrolyte, a micro calorimeter C80 micro calorimeter was used in this paper. The electrolyte samples were heated in argon atmosphere, and the heat flow and pressure performances were detected. It is found that LiPF6 influences the thermal behavior remarkably, with more heat generation and lower onset temperature. LiPF6/EC shows an exothermic peak at 212 ℃ with a heat of reaction -355.4J·g-1.DMC based LiPF6 solution shows two endothermic peak temperatures at 68.5 and 187 ℃ in argon filled vessel at elevated temperature. EMC based LiPF 6 solution shows two endothermic peak temperatures at 191 and 258 ℃ in argon filled vessel.1.0mol·L-1LiPF6/EC+DMC+ EMC electrolyte shows an endothermic and exothermic process one after the other at elevated temperature. By comparing with the thermal behavior of single solvent based LiPF6 solution, it can be speculated that LiPF6 may react with EC, DMC and EMC separately in 1.0 mol·L-1LiPF6/EC+DMC+EMC electrolyte, but the exothermic peak is lower than that of 1.0 mol·L-1LiPF6/EC solution. Furthermore, The 1.0 mol·L-1 LiPF6 /EC+DMC+EMC electrolyte decomposition reaction order was calculated based on the pressure data, its value is n =1.83, and the pressure rate constants kp=6.49×10-2k Pa·-0.83·min-1 .