Catalytic combustion of Qiannan inferior coal added with 1% single catalyst or 1% composite catalyst was studied by thermo-gravimetric experiments, X-ray diffraction analysis, and scanning electron microscope observation. Additionally, kinetic parameters of the coal combustion with or without catalysts were calculated. The results indicated that the apparent activation energy of the coal combustion was reduced with the catalysts. The ignition temperature and burnout temperature of the coal were decreased when catalyzed by the catalysts. The composite catalyst had a more excellent behavior on catalysis. Meanwhile, the X-ray diffraction and scanning electron microscope analysis provided a basis for further mechanism discussion of catalytic combustion.