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The highly elevated concentrations of the rare earth elements and yttrium (REY), U, Mo, Se, and Pb in late Permian coals in some coalfields in Guangxi Province, South China, have been widely investigated; however, the mode of occurrence and enrichment mechanism of these critical elements are still under debate. This study investigates the mineralogical and geochemical compositions of coals and non-coal rocks from the Xian'an Coalfield in Guangxi Province to discuss the geological factors influencing the distribution of critical elements. The mineral in the studied coals consists mainly of quartz, and to a lesser extent, muscovite and kaolinite, with a trace amount of anatase. The coals are significantly enriched in REY, Pb, Se, Mo, and U and display the REY–U–Se–Mo–Pb-enrichment horizon (Horizon I) and U–Mo-enrichment horizon (Horizon II) adjacent to the host rocks or partings. The REY, U, Se, and Pb show organic association while Mo is primarily hosted by Fe-sulfides within Horizon I. The U and Mo have a phosphate affinity within Horizon II. Both the input of pyroclastic and epiclastic materials and the leaching of acidic solutions jointly govern the distribution of the REY–U–Se–Mo–Pb-enrichment horizon (Horizon I) and the U–Mo-enrichment horizon (Horizon II). The concentrations of REY in Horizon I exceed the cutoff grade of REY, and, therefore, the coals in the Horizon I can be regarded as promising raw materials of REY. [ABSTRACT FROM AUTHOR]