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The chemical behaviors of diesel fuel and the effects of aromatic content on combustion characteristics and NOx histories were experimentally investigated using a rapid compression machine and a total-gas sampling device. The aromatic content was changed under constant cetane number. Composition of the individual hydrocarbons, inorganic gases and NOx under various ambient temperatures and fuel injection pressures were analyzed with aromatic-free and aromatic-containing fuels. The results indicate that injected fuel is rapidly decomposed and dehydrogenated during the ignition delay period. The decomposed low boiling-point hydrocarbons consist of mainly unsaturated hydrocarbons such as C2H4, C2H2 and C3H6 at the initial combustion phase. At the diffusion combustion phase, the low boiling-point hydrocarbons consist of mainly CH4.