Chemical laser propulsion (CLP) is accompanied by the release of chemical energy in the process of laser propulsion, which can improve laser propulsion performance. In this article the propulsion performance of POM propellant under the constraint of a cylindrical tube-type thruster in atmospheric and nitrogen environments, respectively, has been conducted experimentally. The results indicate that the ablation masses of a single pulse under two gas environments are close, but the momentum coupling coefficient Cm and specific impulse Isp in atmospheric environment are higher than that in nitrogen environment, which demonstrates an exothermic reaction occurred between the ablation product and the environment oxygen. To learn the mechanism of CLP the molecular spectra for ablation products of POM propellant in atmospheric and vacuum environments are measured and analyzed, respectively, and it reveals that the final product in a vacuum is CH2O, while the final products are CO2 and H2O in the atmosphere. Then the chemical reaction, composition and chemical energy release have been confirmed in the atmospheric environment. By using Arrhenius finite rate chemical reaction model with the code Fluent the flow field evolution of ablation product was simulated numerically. The results show the intensity of chemical energy release is related to the contact and mixing degree of the ablation product and the oxygen in the atmosphere, mixing more fully, the chemical energy released more intensively.