This work aimed to elaborate on the influence of CO2 on the reactivity of CaO with HCl under conditions similar to combustion environment. This study was conducted in an innovated fixed-bed reactor to investigate the influences of simulated CO2 concentrations on the chemistry of CaO with HCl at varied temperatures. Tests of sole CaO carbonation and chlorination were performed in a thermogravimetric analyzer and fixed-bed reactor, respectively, to provide fundamental information for the CaO chlorination experiments in the presence of CO2. The HCl concentrations were continuously monitored in a Fourier Transform Infrared (FTIR) cell and the repeatability tests yielded good results. These results indicated that the presence of CO2 was beneficial for the apparent reaction rates of CaO chlorination performed at 650°C and 700°C, compared with the case of only chlorination; nevertheless, this benefit accompanied a slight reduction of HCl capture capacity. The results were related to the CaO carbonation behavior. On the other hand, further increased CO2 concentrations had no effect on the extent of the chlorination reaction.