Abstract: With on-line coupled thermo-gravimetric analyzer-Fourier transform infrared spectrometer technique, the thermal decomposition of lithium hexafluorophosphate (LiPF₆) and its gas evolution at inert environment (H₂O<10 ppm) were studied under both non-isothermal and isothermal conditions. The results showed that the LiPF₆ decomposition is a single-stage reaction with LiF as final residue and PF₅ as gas product. In addition, its decomposi-tion kinetics was determined as 2D phase boundary movement (cylindrical symmetry) under both non-isothermal and isothermal conditions. Furthermore, the activation energy of LiPF₆ decomposition was calculated as 104 and 92 kJ/mol for non-isothermal and isothermal con-ditions, respectively.