Adding alkali metal salt promoters to calcium-based materials can influence the cycling performance of CaO-based sorbents. So far, most research on alkali metal salts focus on carbonate and chloride salts, while little attention is paid to sulfates. In this paper, we present an in-depth study of the role of Na2SO4 in calcium looping via in-situ experiments and DFT simulations. The results show that the effective conversion rate of Na2SO4-CaO after one cycle is 0.779 with the energy storage density of 2476.1 kJ/kg, while the effective conversion rate of CaO is 0.562 with the energy storage density of 1786.4 kJ/kg. After 80 cycles, the effective conversion and energy storage density of Na2SO4-CaO are lower than CaO, which is attributed to Na+ reducing the surface energy and accelerating the sintering. Moreover, an optimization strategy based on coordination effect among Na2SO4, CaO and inert oxides is proposed to slow down the sintering problems. Among them, Na2SO4-(CaO + ZnO) has the best adsorption performance and energy storage performance and ZnO is cheap, which can be considered a cost-effective sorbent. This work provides a new approach for developing efficient, simple and cost-effective calcium-based materials by simultaneously achieving fast reaction rates and good cycling stability of CaL.