A detailed investigation of the combustion behavior of LiPF6 or LiFSI-based carbonate electrolytes was conducted with the objective of getting better knowledge of lithium-ion battery system fire induced thermal and chemical threats. The well–controlled experimental conditions provided by the Tewarson calorimeter have enabled the accurate evaluation of fire hazard rating parameters such as heat release rate and effective heat of combustion and the quantification of toxic effluents (HF, SO2, NO x …). Results have shown that all the electrolytes tested burn in phases depending on the flammability nature of their mixture constituents. The first stage of combustion is solely governed by the more volatile solvent (linear carbonate) and the influence of adding salt comes into effect predominantly in the second stage. It has been also shown that combustion enthalpy of electrolytes lies in the solvent mixture, irrespective of the salt added. The fire induced toxicity in well-ventilated conditions is found to be mainly dictated by the salt and its chemical structure, showing very limited concerns that emanate from the organic solvents.