Abstract: It is an important way to know about the structure and reactivity of coal by studying the distribution of oxygen-containing functional groups in coking coal.Taking coking coal in Fenxi mining area of Shanxi as the research object, the main types and contents of oxygen-containing functional groups in Fenxi coking coal were characterized by the peak fitting and joint analysis of oxygen structure and carbon structure XPS spectrum.The FTIR spectrum on oxygen functional groups and hydroxyl groups quantitatively analyzed the occurrence of hydroxyl and ether bonds in coal and helped to understand the distribution of hydroxyl structure.The results showed that hydroxyl group, carboxyl group and carbonyl group were the main oxygen-containing functional groups in Fenxi coking coal.The content of hydroxyl groups was the highest, accounting for nearly half of oxygen content in coal, followed by carboxyl and carbonyl groups, ether bond content less.The hydroxyl groups were mainly presented in the form of hydroxyl-hydrogen bonds formed by the electrons on the aromatic ring in the coal, followed by the self-associating hydroxyl hydrogen bonds and the hydroxyl ether hydrogen bonds, and the free hydroxyl groups in the coal were few.The multimer is the concrete manifestation of Fenxi coking coal association structure.