Abstract: The transformation behavior of mineral matters in direct coal liquefaction residue from Shenhua Corporation under gasification atmosphere at high temperatures was examined by X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FT-IR). Mssbauer spectroscopy was also applied to investigate the iron-bearing minerals and the valence distribution of iron in ash at different temperatures. The results show that the major minerals in coal liquefaction residue are quartz, calcium sulfate, millosevichite, pyrrhotite, kaolinite, and calcite. At high temperatures, they become anorthite, gehlenite, maghemite and magnetite. Due to the formation of anorthite, gehlenite eutectic, ash of coal liquefaction residue exhibits low fusion temperature. The iron-bearing minerals characterized in ash include maghemite, magnetite, fayalite, and the vitreous matter. The content of iron in vitreous matter increases with increasing temperature. Meanwhile, Fe²⁺/Fe³⁺ significantly increases from 1.08 to 2.39 as temperature increases from 1 100 to 1 200 ℃ for the reduction of maghemite, and it is not obviously changed above 1 200 ℃. Furthermore, the liquid phase in ash calculated by FactSage increases with temperature owing to the increase of iron in vitreous phase. In hence, high content of iron in ash from coal liquefaction residue is the major reason for its low ash fusion temperatures.