Abstract: Suppressing the spontaneous combustion of lignite is of great significance for safe transportation and efficient utilization of lignite. Taking the Shengli lignite as the research object, two different macerals, inertinite and huminite, were selected by optical microscope, and treated with NaOH respectively to study the relationship between the structure and combustion reaction performance of different macerals and lignite treated with NaOH. The structure of the prepared coal samples was characterized by SEM-EDS, XPS, FT-IR, XRD and Raman, and the changes of the main functional groups were analyzed. The effect of NaOH treatment on the combustion performance of different maceral lignite was investigated by TGA. The results showed that the ignition temperature of huminite lignite was about 10 ℃ earlier than that of inertinite, but the comprehensive combustion characteristic index of inertinite lignite was slightly higher than that of huminite. After the NaOH treatment, the lignite of different macerals showed a hysteresis of combustion, there were two obvious weight losses in the range of 200−500 ℃ and 650−800 ℃, respectively, and the mass loss was mainly concentrated in the second weight loss, in particular, the effect of huminite lignite was more significant, and the temperature corresponding to the maximum combustion reaction rate was about 60 ℃ behind that of inertinite. The kinetic analysis of the combustion process of the coal samples showed that the activation energy of combustion reaction of lignite with different macerals significantly increased after the NaOH treatment, and the huminite lignite was higher than that of inertinite lignite. The XPS/FT-IR results revealed that the contents of carboxylic oxygen-containing functional groups in different macerals of lignite treated by NaOH decreased, the main reason is that in the process of NaOH treatment, Na⁺ interacted with the carboxylic oxygen-containing functional groups in lignite to form the sodium carboxylate structure, and the relative amount of the sodium carboxylate structure in huminite coal was relatively large. It is believed that the inhibitory effect on the combustion of lignite with different macerals is attributed to the stability of the sodium carboxylate structure, and the number of the sodium carboxylate structure formed by combining with Na is the main reason for the difference in its combustion performance. The XRD/Raman analysis indicates that the formation of the sodium carboxylate structure in lignite leads to the increase of the order degree of carbon microcrystalline structure, and the order degree of huminite lignite is higher than that in inertinite.