To investigate the reaction process of aluminized explosives, the rapid reaction in RDX based aluminized explosive powder was stimulated by means of laser ablation, and the emission spectrum distribution in the reaction process was monitored in real time, and the transient temperature of the reaction region was calculated based on the molecular spectrum of AlO. Results show that there are obvious differences in the spectrum distribution and reaction behavior between the early and late stages of aluminized explosives. The early stage is mainly the plasma cooling and the dissipation process of RDX and air formed under la ser ablation.The emission spectrum from the O/H/N element is dominant in this stage, and its spectral line height is exponentially attenuated. The oxidation reaction of Al element is dominant in the late stage, and the reaction has a certain self-sustaining. The spectra of the corresponding intermediates AlO molecules have typical characteristics of persistent and non-monotonic changes. The trend of temperature change is closely related to the development trend of the whole reaction. The temperature of the severe reaction in the early stage is higher and decreases as the reaction continues to weaken.