Perovskite oxides of composition (Sr1-xCax)(Fe0.5Co0.5)O3- were investigated for CO2 absorption properties and were proved to be useful as materials for CO2 absorption in the temperature range from 550 to 850 °C. The absorption rate of CO2 increased with Ca doping. The mechanical treatment of perovskite oxides for several minutes, especially for the oxides containing a small amount of Ca, was found to be effective for activating the oxides for CO2 absorption and for reducing the starting temperature of CO2 absorption by about 80 °C. However, it was not less effective to treat the oxides for a long time. The site distortion due to Sr and Ca ions at site A and the mixed valence states at site B were confirmed to be effective for CO2 absorption at high temperatures. During the absorption of CO2, a spinel compound was formed according to the following reaction: 2(Sr,Ca)(Fe,Co)O2.5 + CO2 (Sr,Ca)CO3 + (Sr,Ca)(Fe,Co)2O4.