Magnesium/polytetrafluoroethylene/Viton (MTV) fuel-rich pyrolants use the atmospheric oxygen as a complementary oxidizer to sustain and alter the performance of the combustion reaction. The flame diffusion characteristics of MTV fuel-rich pyrolants in the atmospheric environment are studied by a high-speed camera (HSC). The flame temperature and combustion components are measured by using remote sensing Fourier Transform Infrared Spectrometer (FTIR). In order to obtain the combustion component distribution more accurately, an aerobic combustion model containing the oxidation reaction of the excess reactant Mg and carbonaceous species with O2 is established in this study. Eddy dissipation concept (EDC) model is applied to the numerical simulation of the three dimensional anaerobic and aerobic combustion field coupled with Realizable k-ε two-equation turbulence model. The research results show that flame temperature is mainly contributed by anaerobic combustion reaction. The flame structure obtained by the aerobic combustion model is closer to the experimental results, and the result of component distribution calculated by aerobic combustion is more consistent with characteristic spectrum. Therefore, the aerobic combustion model is more suitable for describing the actual MTV flame, and the combustion field can be divided into an anaerobic core zone and an aerobic diffusion zone.