This research focused on the hazardous elements in the main coal seam of Huaibei coalfield, China. Through collecting 20 feed coal samples from different coal seams of nine coal mines in the region, and combining with XRF, XRD, ICP-MS, and sequential chemical extraction, the mineral composition and the contents of major elements and HEs for feed coal were analyzed. Compared with previous research results, the enrichment characteristics of HEs in feed coal were revealed. The leaching behaviors of Se, Hg, and Pb in feed coal and coal ash under different leaching conditions were analyzed in depth by using a leaching device independently developed. Results showed that, compared with Chinese coals and World coals, the content of other elements, except Se, Sb, Hg, and Pb, in feed coal of Huaibei coalfield were at the "Normal" level, and no "Low" level elements were found; as the acidity of leaching solution decreased, the relative leaching rate of Se (LSe) was gradually increasing, while the LHg and LPb were not obvious; the LSe in feed coal and coal ash had a great relationship with the modes of occurrence of Se. The difference in the Hg content in the ion exchange state in feed coal may be an important reason for the difference in Hg leaching behavior. However, the content of Pb in feed coal had little influence on its leaching behavior. The modes of occurrence of Pb determined that the LPb in feed coal and coal ash was not high. The LSe increased with the increase in acidity of leaching solution and leaching time. The leaching time was the main influencing factor of the LHg and LPb.