Li8ZrO6 contains a high lithium content and may bear a great ability of CO2 absorption, yet the reports about the properties of CO2 absorption on Li8ZrO6 are few to date for its difficulty in production. In this paper, high-purity Li8ZrO6 is synthesized via a three-step calcination method combined with an effective lithium source and a suitable initial Li/Zr molar ratio. The produced Li8ZrO6 possesses a great CO2 absorption capacity of about 53.98 wt % at 998 K, which could be well-maintained in a wide range of CO2 partial pressures of 0.1-1.0 bar although it decreased gradually during the multicycle process of CO2 absorption-desorption in a 10% CO2 feed stream because of the high working temperature. These properties imply that Li8ZrO6 may be a new option for high-temperature CO2 capture applied in industrial processes such as a steam methane reformer.