To better rule out the complex fire risk related to large format lithium ion cells, a detailed and systematic evaluation, both at component and cell levels, could be an invaluable milestone. Therefore, combustion analysis was conducted for major single organic solvents and their mixtures used in lithium ion battery technology, both in oxygen rich and lean environments using a Tewarson calorimeter. Well controlled test conditions have enabled the determination of key parameters governing the fire induced hazards such as flash point, ease of ignition, heat release rate, effective heat of combustion, specific mass loss rate, as well as the assessment of fire induced toxicity. Moreover, a rule of thumb for the screening of new solvents including the safety perspective such as the Boie correlation and N-factor were introduced for predicting the heat of combustion and combustion kinetics, respectively, prior to conducting any experimental work. Fire induced toxicity of single solvents and their mixtures was also briefly examined by performing toxic gas measurements.