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Spectroscopic measurement and high speed visualization were used in single cylinder, four-stroke DI diesel engine, optically accessible. It was equipped with a four valves head and fully flexible electronic controlled ‘Common Rail’ injection system. The effect of pilot and main injection on combustion process was evaluated. Mixing formation, autoignition and soot formation process were analyzed by broadband ultraviolet-visible flame emission spectroscopy and high-speed digital imaging. The autoignition phase occurred near the tip of the jet and was characterized by strong presence of OH radicals for both investigated conditions The presence of C2 and OH radicals strongly characterized CR diesel combustion process during soot formation and evolution. In particular, high presence of OH concentration for the whole process from the autoignition to the soot formation and successive phases contributes to lower soot levels.