Coal samples in the air for three months were characterized by Thermogravimetric Analysis (TGA). The effect of a PVA oxygen-insulating barrier on the spontaneous combustion of coal was examined. The moisture loss activation energy, oxidation activation energy and combustion activation energy were calculated by an integral method using the Coats-Redfen formula. The results show that the tendency for spontaneous combustion of three coal samples (judged by the activation energy) falls in the order: CYW>YJL>SW. The oxidation activation energy and combustion activation energy of coal protected by the PVA oxygen-insulating barrier increased. A significant increase in the combustion activation energy was noted, especially for the CYW coal where the in-crease was 28.53 kJ/mol. Hence, oxidation of the protected coal samples was more difficult. The PVA oxygen-insulating barrier helps to prevent spontaneous combustion of the coal.