The intermittent and inconsistent nature of some renewable energy, such as solar and wind, means the corresponding plants are unable to operate continuously. Thermochemical energy storage (TES) is an essential way to solve this problem. Due to the advantages of cheap price, high energy density, and ease to scaling, CaO-based material is thought as one of the most promising storage mediums for TES. In this paper, TES based on various cycles, such as CaO/CaCO3 cycles, CaO/Ca(OH)2 cycles, and coupling of CaO/Ca(OH)2 and CaO/CaCO3 cycles, were reviewed. The energy storage performances of CaO-based materials, as well as the modification approaches to improve their performance, were critically reviewed. The natural CaO-based materials for CaO/Ca(OH)2 TES experienced the multiple hydration/dehydration cycles tend to suffer from severe sintering which leads to the low activity and structural stability. It is found that higher dehydration temperature, lower initial sample temperature of the hydration reaction, higher vapor pressure in the hydration reactor, and the use of circulating fluidized bed (CFB) reactors all can improve the energy storage performance of CaO-based materials. In addition, the energy storage performance of CaO-based materials for CaO/Ca(OH)2 TES can be effectively improved by the various modification methods. The additions of Al2O3, Na2Si3O7, and nanoparticles of nano-SiO2 can improve the structural stabilities of CaO-based materials, while the addition of LiOH can improve the reactivities of CaO-based materials. This paper is devoted to a critical review on the development on thermochemical energy storage based on CaO-based materials in the recent years.