A review of the existing optoelectron monitoring devices revealed that the design of optoelectron detectors of the mine atmosphere does not sufficiently take into account the factor of external optical interference. This includes any extraneous source of thermal emission: a source of artificial lighting or enterprises. As a consequence, the optoelectron detectors -based safety systems currently installed at mining sites are not able to ensure properly the detection of the ignition source in the presence of optical interference. Thus, it is necessary to determine the working spectral wavelength ranges from methane and coal dust explosions. The article presents the results of experimental research devoted to the methane-air mixture and coal dust explosion spectral analysis by means of the photoelectric method. The ignition of a methane-air mixture of stoichiometric concentration (9.5%) and coal dust of size characterized by the dispersion of 63–94 microns and concentration of 200 g/m3 was carried out in a 20 L spherical chamber with an initial temperature in the setup of 18–22 °C at atmospheric pressure. Then, photometry of the explosion light flux was conducted on a photoelectric unit. Operating spectral wavelength ranges from methane and coal dust explosions were determined. For the methane-air mixture, it is advisable to use the spectral regions at the maximum emission of 390 and 900 nm. The spectrum section at the maximum emission of 620 nm was sufficient for dust-air mixture. It enabled us to select the wavelength ranges for automatic explosion suppression systems’ launching references. This will exclude false triggering of the explosion suppression system from other radiation sources. The research results will help to improve the decision-making credibility of the device in its direct design. The results will be used in further research to design noise-resistant optical flame detection sensors with a high response rate.