Abstract: A kinetic model of toluene combustion, including 209 species and 1139 elementary reactions, was developed and validated on a fuel-rich premixed toluene flame at 30 Torr. According to the good accordance between simulation and experimental results, it is concluded that this model can satisfactorily predict the concentration profiles of major flame species and the key intermediates in the reaction sequences of decomposition and oxidation of toluene. Rates of production and sensitivity analyses of these key intermediates were performed to draw the major reaction pathways concerning the decomposition and oxidation of toluene. It is shown that toluene is mainly decomposed to benzyl radical, benzene and phenyl radical. These decomposition products can subsequently generate cyclopentadienyl radical and propargyl radical, which are then converted into carbon monoxide via further reactions of decomposition and oxidation. The successful simulation of the decomposition and oxidation processes of toluene will be an initial stage to develop the kinetic models of larger aromatic fuels in the near future, which is useful for the prediction of global combustion characteristics of aromatic components in practical fuels.key word Toluene combustion, kinetic model, decomposition pathways, oxidation pathways