The thermal stability of the neat lithium hexafluorophosphate (LiPF6) salt and of 1molal (m) solutions of LiPF6 in prototypical Li-ion battery solvents was studied with thermogravimetric analysis (TGA) and on-line Fourier transform infrared (FTIR). Pure LiPF6 salt is thermally stable up to 107°C in a dry inert atmosphere, and its decomposition path is a simple dissociation producing lithium fluoride (LiF) as solid and PF5 as gaseous products. In the presence of water (300ppm) in the carrier gas, its decomposition onset temperature is lowered as a result of direct thermal reaction between LiPF6 and water vapor to form phosphorous oxyfluoride (POF3) and hydrofluoric acid (HF). No new products were observed in 1m solutions of LiPF6 in ethylene carbonate (EC), dimethyl carbonate (DMC) and ethyl methyl carbonate (EMC) by on-line TGA–FTIR analysis. The storage of the same solutions in sealed containers at 85°C for 300–420h did not produce any significant quantity of new products as well. In particular, no alkylflurophosphates were found in the solutions after storage at elevated temperature. In the absence of either an impurity like alcohol or cathode active material that may (or may not) act as a catalyst, there is no evidence of thermally induced reaction between LiPF6 and the prototypical Li-ion battery solvents EC, PC, DMC or EMC.