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This present work aimed to investigate the influence of CO₂ on HCl removal using calcined Ca−Mg−Al layered double hydroxides (CaMgAl-LDHs) at medium−high temperature (400−800 °C) in a fixed-bed reactor. It was revealed that a moderate CO₂ concentration (~6%) in the flue gas of the municipal solid-waste incinerators could reduce the HCl capacity of the CaMgAl-layered double oxides (CaMgAl-LDOs). The highest capacity for HCl removal was observed over the CaMgAl-LDOs at 600 °C. However, sintering was also detected when the reaction temperature was below the calcination temperature (600 °C). Moreover, the decreasing HCl adsorption capacity of CaMgAl-LDOs was attributed to the existence of CO₂ in the flue gas, which could efficiently inhibit the decomposition of carbonates as well as the conversion into metal chloride during the HCl removal process.