Carbide slag, a solid waste from the chlor-alkali industry, can be used for CO2 capture and energy storage. Herein, the cyclic reaction activity of Mn/Ce-modified carbide slag under energy storage conditions was studied. The Mn/Ce-modified carbide slag shows energy storage density over 2100 kJ/kg and CO2 absorption capacity of 0.52 g CO2/g sorbent after 30 cycles. Notably, both carbonation and calcination rates are accelerated with the number of cycles. This self-acceleration effect is related to the evolution of oxygen vacancy concentration and texture structure of Mn/Ce-modified carbide slag during the cycles. In the cycles, CaMnO3 in the Mn/Ce-modified carbide slag reacts with the formed CaCO3 in the carbonation stage to produce more Ca2MnO4. The formation of Ca2MnO4 increases oxygen vacancies in the Mn/Ce-modified carbide slag, significantly enhancing its CO2 adsorption capacity. Thus, the release of the increased CO2 in the calcination stage generates more pores in the 10–100 nm diameter range in the modified carbide slag, facilitating rapid carbonation. Thus, the Mn/Ce-modified carbide slag exhibits good prospect for CaO/CaCO3 thermochemical energy storage.