The thermal decomposition of 3,4-bis(4′-aminofurazano-3′) furoxan (BAFF) was studied by DSC, TG, the combination technique of in situ thermolysis cell with rapid-scan Fourier transform infrared spectroscopy (thermolysis/RSFT-IR) and the fast thermolysis probe with rapid-scan Fourier transform infrared spectroscopy (fast thermolysis/RSFT-IR). The result shows that the melting point of BAFF is 168.4°C, the peak temperatures of the two exothermic peaks are respectively 260.4°C and 338.8°C on DSC curve. The apparent activation energy E a and the pre-exponential factor A are respectively 122.21kJmol −1 and 10 9.89 s −1 for major exothermic decomposition process of BAFF. The kinetic equation of major exothermic decomposition for BAFF is dα/dt=10 10.07 exp(−1.46993×10 4 /T)(1−α) [−ln(1−α)] 1/3 . The thermal decomposition gaseous products of BAFF consist of CO 2 , NO 2 , N 2 O and NO. The BAFF is shown by IR spectroscopy to convert to ammonium dicyanamide (NH 4 [N(CN) 2 ]), cyclic azine residues (melamine or melamine-like).