At the atmospheric pressure and at the temperatures between 1,223 and 1,673 K, the CO2 gasification reactivity of seven different carbonaceous materials comprising coal tar pitch coke, petroleum coke, natural graphite, carbon black and three coal chars was investigated by using thermogravimetric analysis. Their crystalline structures were analyzed by X-ray diffraction (XRD). It is found that the reactivity of the chars, pitch coke and petroleum coke produced from liquid phase carbonization, is several times poorer than that of the coal chars produced from solid phase carbonization and even lower than that of natural graphite. At the same time, it is obtained that under the condition of the chemical reaction control, the apparent activation energies of the former are in the range of 135.82-174.92 kJ/mol, while those of the latter are between 89.95 kJ/mol and 110.05 kJ/mol. Besides, the reactivity of the sample has a certain correlation with the crystalline structure of the sample, i.e., the larger the fraction of the relatively better crystalline structure is, the poorer the reactivity of the sample is.