Abstract: The microcrystal structure of Peicheng natural coke (Peicheng mine,Xuzhou), Hanqiao bituminous coal (Hanqiao mine, Xuzhou) and graphite (reagent) was studied by use of X-ray diffraction technique. The gasification characteristic of natural coke with CO2 was studied by thermogravimetry, which is compared with that of bituminous coal. The results show that the microcrystal structure of natural coke and anthracite is similar and there are no 101 diffraction peaks which reflect the three-dimensional structure of crystal lattice and crystallite characteristic of graphitization degree. The gasification reactivity of natural coke is less than that of bituminous coal, but it can get improved by adding the catalyst or increasing the gasification temperature. The CO2 gasification behavior of natural coke with kaliumbased, calciumbased and ironbased catalysts was examined. It is found that the kaliumbased catalyst has the best catalytic performance, and the calciumbased and ironbased catalysts are next. The gasification process of natural coke and bituminous coal can be described by the unreacted coreshrinking model. The kinetic parameters of the gasification reaction were obtained.