CO2 as a gasifying agent can fully or partly replace N-2 for coal gasification. In this study, the effect of the replacement of N-2 by CO2 and the effect of O-2/C molar ratio on gasification performance were investigated via experiments as well as thermodynamic equilibrium calculations. Experiments were performed in a bench-scale self-heated circulating fluidized bed (CFB) gasifier with O-2 volume percentage of 21%. The results showed the Boudouard reaction was strongly enhanced when N-2 in air is replaced by CO2. At the O-2/C molar ratio of 0.39, the replacement of N-2 by CO2 induced an increase in concentration of CO + H-2, yield of CO + H-2, calorific value of product gas, carbon conversion and cold gas efficiency, which is mainly due to the enhancement of Boudouard reaction. Though the elevated O-2/C molar ratio from 0.39 to 0.64 accelerated the combustion proportion, the yield of H-2 + CO was improved in CO2O2 gasification. Meanwhile the cold gas efficiency increased from 43.8% to 58.6% in CO2-O-2 gasification, and showed greater improvement than that in air gasification. The enhancement of Boudouard reaction with the replacement of N-2 by CO2 was further strengthened by the increase in O-2/C molar ratio. The variation of gas composition in CO2-O-2 gasification experiments was predicted by thermodynamic equilibrium calculations, and the increase in the yield of CO + H-2 was verified when N-2 in air was replaced by CO2 in a gasifying agent. (C) 2017 Elsevier Ltd. All rights reserved.