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In this study, light emission and absorption spectroscopic measurement techniques were used to investigate the Homogeneous Charge Compression Ignition (HCCI) combustion process in detail, about which there have been many unclear points heretofore. The results made clear the formation behavior and wavelength bands of the chemical species produced during low-temperature reactions. Specifically, with a low level of residual gas, a light emission band was observed from a cool flame in a wavelength range of 370–470 nm. That is attributed to the light emission of formaldehyde (HCHO) produced in the cool-flame reactions. Additionally, it was found that these light emission spectra were no longer observable when residual gas was applied. The light emission spectra of the combustion flame thus indicated that residual gas has the effect of moderating cool-flame reactions.