Control and online monitoring of combustion have become critical to meet the increasingly strict pollutant emission standards. For such a purpose, optical sensing methods, like flame emission spectrometry, seem to be the most feasible technique. Spectrometry is capable to provide information about the local equivalence ratio inside the flame through the chemiluminescence intensity ratio measurement of various radicals. In the present study, a 15 kW atmospheric burner was analyzed utilizing standard diesel fuel. Its plain jet type atomizer was operated with both air and steam atomizing mediums. Up to now, injection of steam into the reaction zone has attracted less scientific attention contrary to its practical importance. Spatial plots of OH*, CH*, and C 2 * excited radicals were analyzed at 0.35, 0.7, and 1 bar atomization gauge pressures, utilizing both atomizing mediums. The C 2 * was found to decrease strongly with increasing steam addition. The OH*/CH* and OH*/C 2 * chemiluminescence intensity ratios along the axis showed a divergent behavior in all the analyzed cases. Nevertheless, CH*/C 2 * chemiluminescence intensity ratio decreased only slightly, showing low sensitivity to the position of the spectrometer. The findings may be directly applied in steady operating combustion systems, i. e., gas turbines, boilers, and furnaces.