In this work, a methodology based on the combined use of a multilayer perceptron model fed using selected spectral information is presented to invert the radiative transfer equation (RTE) and to recover the spatial temperature profile inside an axisymmetric flame. The spectral information is provided by the measurement of the infrared CO2 emission band in the 3-5 μm spectral region. A guided spectral feature selection was carried out using a joint criterion of principal component analysis and a priori physical knowledge of the radiative problem. After applying this guided feature selection, a subset of 17 wavenumbers was selected. The proposed methodology was applied over synthetic scenarios. Also, an experimental validation was carried out by measuring the spectral emission of the exhaust hot gas plume in a microjet engine with a Fourier transform-based spectroradiometer. Temperatures retrieved using the proposed methodology were compared with classical thermocouple measurements, showing a good agreement between them. Results obtained using the proposed methodology are very promising and can encourage the use of sensor systems based on the spectral measurement of the CO2 emission band in the 3-5 μm spectral window to monitor combustion processes in a nonintrusive way.