Abstract: To alleviate the supply pressure of traditional rare earth resources and fully exploit the utilization value of coal-based rare earths, this study focuses on coal slime from the Xuangang mining area of the Ningwu coalfield in Shanxi. The rare earth element (REE) content, occurrence characteristics, and the feasibility of flotation pre-concentration were systematically investigated. A combination of sequential chemical extraction and Spearman correlation analysis was employed to analyze the REE content and occurrence modes. Based on these characteristics, flotation pre-concentration experiments were conducted by regulating flotation conditions (pH = 10, oleic acid dosage of 2 kg/t). The results indicate that the coal slime from the Xuangang mining area is a light REE-enriched sample with significant development potential. The total REE content is 344.23 μg/g, with a light-to-heavy REE ratio of 10.02. The critical REE content is 117.19 μg/g, and the outlook coefficient is 0.89. Spearman analysis shows that erbium (Er) is positively correlated with aluminum (Al) and silicon (Si), occurring in kaolinite and quartz in the form of silicate/aluminosilicate-bound states. The other 14 REEs exhibit strong correlations with major elements such as iron (Fe) and calcium (Ca), primarily existing as carbonate/phosphate-bound states within calcite. After flotation pre-concentration, the calcite content in the concentrate increased significantly, and the neodymium (Nd) content rose to 85.44 μg/g, an increase of 32.44 μg/g compared to the raw coal slime. By integrating sequential chemical extraction with Spearman correlation analysis, this study clarifies the specific carriers and occurrence modes of coal-based REEs. The successful enrichment via targeted flotation condition regulation validates the feasibility and effectiveness of flotation technology for coal-based REE recovery, providing a theoretical basis and technical support for the development of these resources.