To know the sustainable performance of calcium-based adsorbents is one of the important aspects to realize efficient and economical carbon capture, and to systematically study the properties of natural adsorbents is conducive to their industrialization. The cyclic calcination and carbonation characteristics of a typical natural limestone were investigated using a thermal gravimetric analyzer. Two kinds of over-sintering conditions were selected to emphatically study the cyclic separation of CO₂ from limestones through prolonging the calcination time and increasing the calcination temperature. The results showed that the untimely end of the chemical reaction control stage caused by excessive sintering is the direct reason for the reduction in cyclic carbonation conversion, and the changes in surface morphology of calcined products due to pore collapse and fusion are the fundamental reasons for the reduction in cyclic carbonation conversion. The excessive sintering caused by extending the calcining time or increasing the calcining temperature has great inhibition on this cycle only; the inhibition decreases rapidly in subsequent cycles. In addition, SEM and BET–BJH tests further confirm the influence of the over-sintering phenomenon. With the further increase in cycle number, the early excessive sintering has certain stimulative effects on the subsequent carbonation reaction. It is expected to provide a reference for the subsequent research and development of natural calcium-based adsorbents.