The thermal decomposition characteristics and the thermal safety parameters of 2,2-di(tert-butylperoxy)butane (DBPB) was investigated by differential scanning calorimetry (DSC). The apparent activation energy (E-a) was evaluated by three different kinetic analysis methods based on the DSC experimental results. By the method of Malek, Zhuravlev-Lesokhin-Tempelman (Z-L-T) equation was the most probable mechanism function of DBPB decomposition. Furthermore, for the safety of storage and transportation, the self-accelerating decomposition temperature (SADT) of 50 kg standard packaged 50% w.t. DBPB solution was calculated by Semenov model. And the decomposition products were separated and identified by gas chromatograph/mass spectrometer (GC/MS). The decomposition process of DBPB was inferred which may help us to interpret the decomposition mechanism of di-functional peroxides. Finally, the findings of this study could do a contribution to preventing the thermal hazardous accidents, which would happen during DBPB chemical process, transportation and storage.