The partition evolution of parent calcium carbonate (CaCO3) and its effect on the catalyzed sintering of regenerated CaO during calcium looping cycles were investigated. The carbonation reaction rate has a heterogeneous distribution either in the particle radial direction or in the same layer, which causes the partition structure evolution of CaCO3 from overall dense structure to region partition structure. Both the residual and sintering of regenerated CaO were enhanced with the structural evolution of carbonate precursor. Within the first five cycles, an initial structural division of the CaCO3 matrix occurs accompanied by a sharp decrease in the number of mesopores, indicating a dependence of the CO2 capture ability on the structure evolution of the sorbent skeletal.