By controlling the milling time and the mass proportion of Al to Ti, the metallic amorphous Al/Ti spherical particles (Al/Ti alloy) with mean size of 3.76um were fabricated by mechanical milling method. The catalysis effects of the as prepared Al/Ti alloy on the thermolysis of five explosives, i.e. Hexanitrostilbene (HNS), 2,6-diamino-3,5-dinitropyrazine-1-oxide (LLM-105), Cyclotrimethyltrinitroamine (RDX), Cyclotetramethylenetetranilamine (HMX), and Hexanitrohexaazaisowurtzitane (CL-20) were probed using thermal analysis. For HNS, the decomposition peak temperature (Tp) of the doped HNS with the alloy decreased by 6.9°C, 7.2°C, 4.8°C and 5.2°C respectively at different heating rates compared with raw HNS. Similarly, for the rest four explosives, the Tp value of the doped explosives with the alloy mainly decreased compared with the respective raw explosive. All thermodynamic parameters of the explosives were calculated. It indicated that the active energy (EK) of the doped explosives with alloy markedly declined by 52.4 kJ.mol^-1 (HNS), 41.6 kJ.mol^-1 (LLM-105), 8.6 kJ.mol^-1(RDX),48.4 kJ.mol^-1(HMX), and 46.7 kJ.mol^-1(CL-20), respectively. It is ascertained that doping spherical amorphous Al/Ti alloy can promote the thermal decomposition of explosives.