The influence of several process parameters on the calcination of a naturally occurring limestone and a precipitated mesoporous calcium carbonate (CaCO3) sorbent structure to calcium oxide (CaO) is detailed in this study. CaCO3 calcination is an integral part of a multicyclic carbonation-calcination reaction (CCR) process that separates carbon dioxide (CO2) from high-temperature gas mixtures into a pure CO2 stream. Maintenance of high sorbent reactivity over repeated CCR cycles reduces the capital and operating cost of the CCR process. A lower calcination temperature, required to maintain high sorbent reactivity, reduces the calcination rate of CaCO3. This study investigates various process conditions such as subatmospheric calcination, sorbent dispersion in a rotary calciner, use of a high thermal conductivity sweep gas, etc. in enhancing the calcination rate at lower calcination temperatures. The high-temperature gas-solid carbonation studies of the resulting CaO sorbent prove the necessity to maintain a high porosity structure during limestone calcination.