A polymeric template consisting of polystyrene microbeads was used to provide the macroporous structure of synthesized CaO-based sorbents. It was found that the pore size distribution of prepared and calcined sorbents drastically depends on the amount and particle size of the template used, as well as on the sorbent preparation conditions. The macroporous structure formed after the template removal significantly increases the rate of both recarbonation and decomposition reactions. The decomposition rate of the sorbent produced from a 40% templated composite was an order of magnitude higher than the rate of a reference sample produced in the absence of the template. In this way, the template approach seems to be a perspective technique to prepare CaO-based sorbents with enhanced recarbonation/decomposition performance.