In situ monitoring of chemical species from the combustion pulverized coal in high-temperature air is examined using several different spectroscopic diagnostic at different equivalence ratios. Two-dimensional (2D) distributions of flame temperature were obtained using a thermal video camera. The experimental results showed the temperatures to range from low to 1400 °C under various conditions of fuel-lean, stoichiometric, and fuel-rich. The highest temperature and flame stability were obtained under fuel-lean combustion condition. The chemical species generated from within the combustion zone were analyzed from the spontaneous emission spectra of the flame in the Ultraviolet–visible (UV-Vis) range. The spatial distribution of NO, OH, and CN were identified from the spectra. The 2D distribution of emission intensity visualized and recorded for NO, OH, and CN revealed high-temperatures close to the root of the flame that rapidly dispersed radially outward to provide very high temperatures over a much larger volume at further downstream locations of the flame.