Fly ash usually contains a considerable amount of toxic elements that can be leached into the environment, thereby easily leading to serious contaminations. In this work, the leaching behaviors of poisonous elements including boron (B), phosphorus (P), vanadium (V), chromium (Cr), arsenic (As), selenium (Se), molybdenum (Mo), antimony (Sb), and tungsten (W) from fly ash were explored by sequential extraction. Importantly, the associations of these elements in fly ash were discussed based on their leaching and X-ray absorption near-edge structure (XANES) results. From the XANES results, it was observed that V(IV), Cr(III), As(V), Se(IV), and W(IV) were their main states of existence in fly ash. In terms of leaching results, large amounts of Mo and W were leached into pure water, which indicated their high mobilities. Furthermore, the occurrence of Mo in fly ash was mainly in the form of oxides, and W had complex associations including WX (X can be monovalent anions), its reduction state or association with the elements that can be oxidized, and existence in silicates. B was as easily released into the environment as Mo and W. It can have several associations with the other cations, such as Ca, Na, and Mg, and occurs in silicates. In contrast, most of the Cr and Sb were locked in silicates, indicating that they were very stable in fly ash. In addition, P, V, and As can exist within the structure of silicates as well. However, a considerable amount of them leached in the reduction step with a low pH. Hence, they can be associated with Ca, Na, Mg, or Fe. In terms of Se, oxidation processes played an important role in controlling its leaching because of the oxidation of Se(IV) to Se(VI). Calcium selenite should be the predominant form of Se in fly ash.