We have theoretically studied the NF3 = NF2 + F, NF2 + F = NF + F-2, and NF2 + F = NF2 + F reactive processes. More precisely, we have evaluated the thermal rate constants (TRC), with the Wigner and Eckart tunneling corrections, minimum energy path, and the intrinsic reaction coordinates of these systems. The NF3 = NF2 + F conventional and Wigner TRCs agree very well with experimental data available in the literature for a wide range of temperatures. This study gives a first step to understand and determine the correct decomposition path of nitrogen trifluoride (NF3).