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A spectroscopic diagnostic system was designed to study the effects of different engine parameters on the chemiluminescence characteristic of HCCI combustion. The engine parameters studied in this work were intake temperature, fuel delivery method, fueling rate (load), air-fuel ratio, and the effect of partial fuel reforming due to intake charge preheating. At each data point, a set of time-resolved spectra were obtained along with the cylinder pressure and exhaust emissions data. It was determined that different engine parameters affect the ignition timing of HCCI combustion without altering the reaction pathways of the fuel after the combustion has started. The chemiluminescence spectra of HCCI combustion appear as several distinct peaks corresponding to emission from CHO, HCHO, CH, and OH superimposed on top of a CO-O continuum. A strong correlation was found between the chemiluminescence light intensity and the rate of heat release.