AbstractThe effect of CaCO3 particle size on the viscosity of slurry, phase formation, microstructural evolution, and performances of the water‐soluble CaO‐based ceramic core sintered at different temperatures was systematically investigated and discussed, and the particle gradation orthogonal experiments were used to adjust flexural strength, water‐soluble rate, shrinkage rate, apparent porosity, and hygroscopicity rate. The results showed that the finer particle size increased the effective contact area between CaO and SiO2, which promoted the generation of CaO–SiO2 system phase and the dense microstructure in the sintered CaO‐based cores. The higher sintering resulted in dense microstructure. The optimal gradation scheme included 28 wt.%, 56 wt.%, and 16 wt.% CaCO3 powder with D50 = 11.0 µm, 6.17 µm, and 4.62 µm, respectively, and the resulting flexural strength was 9.57 MPa, water‐soluble rate was 65.37 g/h in 60°C water, shrinkage rate was 8.62%, porosity rate was 38.85%, presenting a well‐balanced comprehensive performance, which is significant for the complex internal castings.