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A numerical simulation study on chemical kinetics of engine combustion fueled with biodiesel was performed by using zero dimension single-zone model coupled with a detailed kinetic model. The main pathway of biodiesel combustion was obtained by analyzing key elementary reactions, production rates of key intermediate species and radicals of oxidation process under engine boundary condition. The results showed that, the combustion of biodiesel consisted of a low temperature heat release period and a high temperature heat release period. The dehydrogenation reaction was main pathway of biodiesel consumption in low temperature stage, and the decomposition of the fuel and dehydrogenation reaction were main pathways in high temperature stage. OH radical played a leading role in the dehydrogenation of fuel both in low and high temperature stage.