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The development of methanol/diesel dual-fuel engines urgently requires further study on chemical kinetic models for binary fuels. Ignition delay of lean and stoichiometric methanol/n-heptane mixtures (30/70, 50/50, 70/30, and 90/10) diluted with argon was investigated at high temperature (T = 1195 K–1514 K) and low pressure (p = 2 bar) using an aerosol shock tube and a detailed LLNL3.1 mechanism. The results indicated that LLNL3.1 mechanism agreed well with the current measurements. An increase in methanol can accelerate the ignition process at Ф = 1, because of the key radical---HO2, produced by CH2OH + O2=CH2O + HO2, which was affected by the methanol concentration. HO2 would subsequently attack the parent fuels and combine with H radical (HO2+H = 2OH), leading to the booming radical pool. For lean mixtures, n-heptane promoted the reactivity of system due to its high sensitivity to reaction H + O2=O + OH. The higher initial O2 concentration expedited this reaction and shortened the IDT. Besides, both methanol and n-heptane undergo H-abstraction reaction mostly by H radical, however, these reactions showed an inhibition effect on reactivity. This is caused by the competition for H radical between O2 and the parent fuels. Also, the fuel radicals, produced by C7H15-3, had a low decomposition reaction rate thus slowing down the chain branching and suppressing the reactivity of system. • Ignition characteristics of methanol/n-heptane mixtures were studied by shock tube and mechanism. • Methanol accelerated the auto-ignition for stoichiometric mixtures due to the HO2 radical. • N-heptane promoted the reactivity for lean mixtures due to its high O2 sensitivity. • H-abstraction of the parent fuels by H radical showed an inhibition on auto-ignition. [ABSTRACT FROM AUTHOR]