Surface property plays a very important role on coal hydrophobicity which determines flotation behavior of fine coals. However, coal spontaneous combustion makes coal suffer both oxidation and high temperature heating processes. Coals from the outside of coal piles primarily suffer oxidation process (or combustion process) while coals from the inside of coal piles primarily suffer high temperature heating process. It is necessary to investigate the changes in surface properties of coal before and after high temperature heating process. In this investigation, X-ray photoelectron spectroscopy (XPS), scanning electron microscope (SEM), surface area (BET) and contact angle measurements were used to indicate the changes in surface properties of anthracite coal before and after high temperature heating process. Throughout this study, surface properties of coal can be changed significantly after high temperature heating process. Meanwhile, coal hydrophobicity can be also reduced after high temperature heating process.