To understand effects of inherent mineral matters on the evolution of char structure, the microcrystalline structures of chars from the pyrolysis of raw, HCl-washed (CW) and HCl & HF-washed anthracites (CFW) were investigated by X-ray diffraction (XRD) respectively. Stacking height (Lc), interlayer spacing (d(002)) and crystallite width (La) were used as parameters for char structure estimation. The results showed that with increasing contents of inherent mineral matters, Lc of char decreased, whereas don and La increased. To study effects of a single inorganic matter, CFW was impregnated with Al2O3, SiO2, and CaO respectively. It was found that all of them (oxides) have resulted in the decrease in Lc and increase in La and d(002). Differing from Al2O3, SiO2, and CaO, the introduction of Fe2O3 has caused the reduction for both La and Lc values simultaneously, especially when the Fe2O3 contents in the coal were high.