Degradation behavior of combustible fuel is the core factor in determining combustion characteristics. To investigate the effect of ambient atmosphere on the pyrolysis process of polyoxymethylene (POM), the pyrolysis mechanism of POM was studied with thermogravimetric analyzer tests and Fourier transform infrared spectroscopy tests. The activation energy, reaction model, and estimated lifetime of POM pyrolysis under different kinds of ambient gases have been estimated in this paper based on different results of the kinetics. The activation energy values, obtained with different methods, were 151.0–156.6 kJ mol⁻¹ in nitrogen and 80.9–127.3 kJ mol⁻¹ in air. Then, based on the Criado analysis, the pyrolysis reaction models of POM in nitrogen were found to be mastered by the “n + m = 2; n = 1.5” model, and by the “A3” model in air. The optimum processing temperature for POM was estimated, with a range from 250 to 300 °C in nitrogen and from 200 to 250 °C in air. IR analysis revealed that the significant difference in POM decomposition between N₂ and O₂ atmospheres is the formation of isocyanate group or carbon dioxide. Combustion parameters of two POMs (with and without flame retardants) obtained using cone calorimetry revealed that flame retardants can effectively improve the ignition time, smoke release rate, and other parameters of POM. The outcomes of this study will contribute to the design, storage, and transportation of polyoxymethylene.