Fluorine (F) is a topic of great interest in coal-combustion related endemic fluorosis areas. However, little extent research exists regarding the environmental geochemistry of toxic elements that are enriched in coals and coal wastes in traditional endemic fluorosis areas, particularly focusing on their occurrences and mobilities during the weathering -leaching processes of coals and coal wastes in the surface environment. This paper addressed the issue of toxic elements in coals and coal wastes in the Three Gorges Region, Southwest (SW) China, where endemic fluorosis has historically prevailed, and investigated the distribution, occurrence, mobility features, and associated potential health risks. For this purpose, a modified experiment combined with long-term humidity cell test and column leaching trial was applied to elucidate the mobility of toxic elements in coals and coal wastes. In addition, sequential chemical extraction (SCE) was used to ascertain the modes of occurrence of toxic elements. The results demonstrated that the contents of toxic elements in the study area followed the order: stone coals > gangues > coal balls > coals. Furthermore, modes of occurrence of toxic elements were obviously different in coals and coal wastes. For example, cadmium (Cd) was mainly associated with monosulfide fraction in coals, molybdenum (Mo) and arsenic (As) were mainly associated with carbonate and silicate in coal gangues and stone coals, chromium (Cr) mainly existed in silicate and insoluble matter in coal gangues and coal balls, thallium (Ti) mainly occurred in organic matter in stone coals and sulfide in coals, and the occurrence of antimony (Sb) varied with different kinds of samples. Moreover, a large amount of toxic elements released to the leachates during the weathering and leaching process, which might pollute the environment and threaten human health. Based on the geo-accumulation index (I-geo), single factor index (P-i) and Nemerow index (P-N), soils in the study area were mainly polluted by Cd, which constituted a potential risk to locally planted crops.