2-methylfuran (2MF) and 2,5-dimethylfuran (2,5-DMF) are new generation of green biofuels, and because of their high octane number and similarity to gasoline in energy density, they are very potential octane boosters. However, the effect of molecular structure of furans on the knocking behavior of fuels is still unclear in the temperature range of 298 K–1198 K. Therefore, in this paper, the key free radicals and their reaction sites in the two fuel auto-ignition paths of 2MF and 2,5-DMF are studied in the range of low to intermediate temperature by DFT method. We found that DMF22j and 2MF22j produced by methyl dehydrogenation on the side chain of furan ring are the most stable radicals produced by H-abstraction reaction. For 2MFnOH, the reactivity of 2MF increased after OH addition and the addition reaction with O2 was most likely to occur when OH was bound to C2 site.
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