A differential scanning calorimeter (DSC) was used to perform a thermal stability study of the LiPF6–EC:EMC electrolyte. The effect of different variables on its thermal stability was evaluated: salt (LiPF6) concentration effect, solvents, EC:EMC ratios, and heating rates. Hermetically sealed and crimped DSC pans were used during the experiments. The results indicate that the salt concentration, solvent concentration, and heating rates play an important role in the thermal stability of the LiPF6–EC:EMC electrolyte.