In the current study, the volume-sintering model was implemented for the simulation of sorption/desorption and textural evolution of the set of CaO-based sorbents with broad differences in porous structure. The porous structure of the materials was modeled with the dense random packing of spheres using the Lubachevsky–Stillinger compression algorithm. The simulated packages were fitted to the parameters of the porous structure of real templated and non-templated CaO-based sorbents. The sintering of the packages during sorption/regeneration cycles was carried out based on the assumptions of the lattice diffusion mechanism and the sintering rate of CaCO3 being higher than that of CaO in the proposed model. The obtained model predicts well the dependence of textural changes and the recarbonation extent on the number of the sorption/regeneration cycles for the sorbents with different porosity and grain size.