A good knowledge of the kinetics of combustion of biodiesel fuels is required for predicting combustion performance and emission characteristics of IC engines and gas turbines. The kinetic of oxidation of rapeseed oil methyl ester (RME) was studied in a jet-stirred reactor for the first time. RME is a complex mixture of C14, C16, C18, C20, and C22 esters. The complexity of this fuel is such that it is difficult to propose a detailed kinetic scheme for its oxidation. It is preferable to use a surrogate model-fuel of simple and well characterized composition for the modeling. Based on the present experimental results, n-hexadecane is proposed to represent RME in the computations. The chemical kinetic reaction mechanism consisted of 225 species and 1841 reversible reactions. The kinetic modeling gives a good description of the experimental results: (i) a very good modeling of the relative importance of the olefins (C2–C6) was obtained, (ii) the experimental and simulated reactivity of RME are in good agreement. The effectiveness of using surrogate model-fuels for modeling the combustion of complex commercial fuels, as demonstrated before for kerosene and a diesel fuel is confirmed by the present study.