Abstract Low temperature oxidation of coal will result in coal spontaneous combustion in mined-out areas. We proposed to use ionic liquids to inhibit the coal spontaneous combustion in this paper. In order to study the inhibiting effect of ionic liquid (IL) on coal oxidation, we successfully dissolved bituminous coal samples in six kinds of imidazolium based ionic liquids, [AOEmim][BF4], [HOEmim][BF4], [Amim][Cl], [Emim][AC], [Bmim][AC] and [Bmim][OTf]. The functional groups in the coal samples pre-treated by different ILs were detected by Fourier Transform Infrared Spectroscopy (FTIR) in detail. It is found that the ILs are capable of breaking the associated hydroxyls into dissociated hydroxyls. And during the interaction between coal and ILs, the carboxyl groups have been created. Thermo Gravimetric experiment results show that the weight loss ratios of the IL-treated coals were less during 20–400°C stage, compared with the IL-untreated coal, which indicates that most of the easily reductive groups effectively dissolved in the ionic liquids. According to the exothermic rate curves and the computed activation energy values, it is demonstrated that the [Bmim][OTf] and [Bmim][AC] make better effect than the other ILs for depressing the oxidation rate of bituminous coal.