Calcium oxide (CaO) has been investigated as a high-temperature performance sorption material for carbon capture due to its high carbon dioxide (CO2) capacity, low cost, and environmental benignity. Unfortunately, commercialized application of CaO materials has been hindered by severe capacity loss during cycling operations. In an attempt to overcome these problems, this study investigated the effects of adding zirconia-based ceramic dopants and coating sorbents with highly crystalline zirconium dioxide (ZrO2) layers derived from the hydrolysis of zirconium butoxide to control the growth of ZrO2 crystals. Uncoated natural Cadomin delivered a high CO2 capture capacity of more than 13 mol CO2/kg, while the zirconia-coated sorbents showed excellent cycling stability corresponding to a maximum capacity of retention of 79% after 21 cycles at high temperatures. More importantly, the highly crystalline ZrO2-coated sorbents doped by zirconia-based sorbents exhibited a significantly lower decay capacity compared to the uncoated sorbents, which could be attributed to the formation of a perovskite structure that is resistant at high temperatures and a high-temperature-resistant ceramic layer through the solid-state reaction of the highly mesoporous crystalline ZrO2 layer with CaO. These results shed light on the development of sorbents with special structures and superior chemical and mechanical properties for high-performance calcium looping or regenerative calcium cycle processes. (Graph Presented).