The decline in CaO/Ca(OH)2 heat storage performance of CaO-based material with the number of cycles due to its fast expansion and fragmentation is an problem in the fluidized bed reactor. In this paper, a novel SiO2-coated CaO particle was manufactured from limestone and silica sol via wet-mixing method. Exothermic performance (such as exothermic temperature, effective hydration conversion and volumetric energy density) and structural stability of SiO2-coated CaO particles in a fluidized bed reactor were studied. The effects of SiO2 addition and calcination temperature on the exothermic performance and structural stability were analyzed, respectively. The results show that the mass ratio of limestone to silica sol of 1:1 and calcination temperature of 850 °C are recommended for the preparation of SiO2-coated CaO. The SiO2 layer is observed on the surface of the CaO. SiO2-coated CaO particles exhibit superior structural stability than uncoated CaO particles. The SiO2 coating reduces the increase of average particle size during 10 cycles from 33 % to 11 %. After 10 heat storage cycles, SiO2-coated CaO particles achieve a reduction of 45.4 % in expansion rate and 48.5 % in attrition rate compared with uncoated CaO particles, respectively. The volumetric energy density of SiO2-coated CaO particles after 10 cycles is 33.2 % higher than that of uncoated CaO particles. The highest exothermic temperature of SiO2-coated CaO particles after 10 cycles reaches 455.4 °C (steam partial pressure @ 60 kPa). The SiO2-coated CaO seems a promising candidate for the CaO/Ca(OH)2 thermochemical heat storage in the fluidized bed rector.