A nonintrusive low-cost sensor based on silicon photodiode detectors has been designed to analyze the formation and behavior of excited ${\mathrm{CH}}^{*}$ and ${{\mathrm{C}}_2}^{*}$ radicals in the combustion process by sensing the spectral emission of hydrocarbon flames. The sensor was validated by performing two sets of experiments for both nonconfined and confined flames. For a nonconfined oil flame, the sensor responses for the axial intensity were highly correlated with the measurements obtained with a radiometer. For confined gas flames the ratio between the signal corresponding to ${{\mathrm{C}}_2}^{*}$ and ${\mathrm{CH}}^{*}$ was successfully correlated with the CO pollutant emissions and the combustion efficiency. These results give additional insight on how to prevent an incomplete combustion using spectral information. The fast response, the nonintrusive character, and the instantaneous measurement of the needed spectral information makes the proposed optical sensor a key element in the development of advanced control strategies for combustion processes.