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To determine the auto-ignition and combustion mechanisms and the components of syngas that are applicable to homogeneous charge compression ignition (HCCI) engines, the combustion characteristics and the chemical reaction process in an HCCI engine were studied numerically and experimentally using mock syngas with various mixtures of the fuel components. The mock syngas consisted of hydrogen (H2) and carbon monoxide (CO) as the main combustible components, nitrogen (N2) and carbon dioxide (CO2) as incombustible components and a small amount of methane (CH4), assuming the composition of the gas was produced from wood by thermochemical conversion processes. The oxidation reaction process was analyzed numerically using CHEMKIN-PRO. Further experiments were conducted to investigate the validity of the calculated results. Primarily, the effects of hydrogen and carbon monoxide on auto-ignition and combustion were investigated.