Low-rank coal contains abundant hydroxyl, carboxyl and alkyl side chains, and reactions related to these groups are the main reason for the spontaneous combustion of low-rank coal. Here, two different low-rank coals (BRXL, YJL52) are selected. Firstly, the ignition temperatures of the coals are determined by thermogravimetric method. Secondly, the coals are heated at 100°C temperature intervals before the ignition temperature in the thermogravimetry, and infrared measurement is performed to explore the changes of these groups. Combining previous studies in the literatures with infrared analysis, it is found that reactions related are as follows: phenolic hydroxyl converting into alcoholic hydroxyl, alcoholic hydroxyl further oxidizing to carboxyl, and carboxyl decarboxylating into alkyl side chains. After that, the changes of phenolic hydroxyl and carboxyl on the surface of the coal at 100°C temperature intervals are determined by titration, which further reveal the main reactions occurred in every temperature interval. Additionally, the actual heat release in different temperature ranges is discussed with the reaction enthalpies of the above-mentioned main reactions. As a result, the key temperature stage that causes spontaneous combustion is found. The screening study in this paper on the reaction of low-rank coal before spontaneous combustion provides a theoretical basis for the control of spontaneous combustion of low-rank coal.