The Huainan and Huaibei coalfields, as two of the most important coal-producing areas in China, have long attracted significant attention regarding coal resource mining and utilization. As an important environmental resource, coal requires a thorough understanding of the content, occurrence modes, and enrichment factors of its trace elements, which is crucial for geochemical characterization, efficient utilization, and environmental protection. Based on a comprehensive review of domestic and international literature and previously published laboratory data, we analyzed the coal quality and conducted a geochemical study of trace elements in the Huainan and Huaibei coalfields, focusing on: (i) distribution and enrichment characteristics of trace elements in different coal seams; (ii) comparison of trace elements between the two coalfields; (iii) modes of occurrence; and (iv) controlling factors of enrichment. Our findings show that As, B, Be, Cd, Sb, Se, and Sn are slightly enriched in Huainan coal, whereas Be, Cd, Cr, Cu, Hg, Ni, Pb, Sb, Se, Sn, U, and V are slightly enriched in Huaibei coal, with considerable variation among seams. Huainan coal is enriched in light and medium rare earth elements, whereas Huaibei coal is enriched in heavy rare earth elements. Vertically, trace elements in the coal-bearing strata exhibit three overall trends from bottom to top: decreasing, increasing, and increasing then decreasing. Elemental associations exhibit both commonalities and differences across seams. Trace elements in these coalfields occur in various forms, including silicate-bound, sulfide-bound, carbonate-bound, organically bound, ion-exchangeable, and water-soluble forms. Mineralogical transformations in coal are also closely related to trace element redistribution. The degree of trace element enrichment is controlled by multiple factors, including parent rocks in the terrigenous area, sedimentary environment, structure, and magmatic-hydrothermal activity. A deeper understanding of these trace element geochemical characteristics is essential for efficient coal utilization, environmental protection, and advancing green coal chemistry.