The thermodynamics of possible reactions, including gasification and reduction reactions, in carbon carbon dioxide sodium or potassium carbonate systems was analyzed first. And then, the gasification reactions of graphite and coke with CO2 in this system were studied kinetically by temperature programmed thermogravimetry. The results showed that the carbon conversion curve shifted to a lower temperature zone after Na2CO3 or K2CO3 was added, and graphite was more susceptible than coke to be catalyzed by Na2CO3 or K2CO3. Ten kinetic equations were adopted to simulate the reaction process using the method of Coats-Redfern. The Avrami-Erofeev equation was found to be the most probable kinetic equation, with which the values of activation energy and frequency factor were calculated. The kinetic simulation indicated that the activation energy of coke carbon had been activated to the lowest level by its inner factors, thus it was difficult to be reduced by adding Na2CO3 or K2CO3. The kinetic compensation effect was confirmed to exist in both graphite gasification and coke gasification. X-ray diffraction and Raman spectra were used to characterize the inner difference between graphite and coke, which showed that coke carbon structure was greatly different from graphite structure because of its highly disordered and heterogeneous carbon structure.