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An investigation on oxygen-equilibrium of laser ignition of energetic materials was carried out through experiments. The threshold energy of laser ignition of several systems such as Zr/KClO 4, Ti/KClO 4, and Mg/KClO 4 were measured with different system composition. The results show that the mass ratio of initial mixture powders has a significant effect on the threshold energy of ignition. The threshold energy presents a minimum with increasing mass ratio, which corresponds to an oxygen-rich system composition. That is, an oxygen-rich composition is favorable to laser ignition. The ignition requires lower threshold, or energetic materials have relatively higher laser sensitivity. Also the findings were theoretically analyzed.