Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) were used to indicate the surface properties of Inner Mongolia high-ash coal in China. The results of FTIR and XPS showed that there were few hydrophilic functional groups but many hydrophobic functional groups on high-ash coal surface. Meanwhile, the primary minerals in coal were kaolin, such as SiO2 and Al2O3. Throughout this paper, it was found that the natural hydrophobicity of Inner Mongolia coal was high but the kaolin may have negative effects in the clean coal quality.