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CaZrO3 samples were prepared by in situ decomposition pore forming technology in this paper. The influence of calcia/zirconia molar ratio and heating treatment on the microstructure and thermal conductivity of the sintered samples were investigated. The phase analysis of CaZrO3 samples was detected by X‐ray diffraction, and the microscopic morphology of CaZrO3 was observed by scanning electron microscope combined with energy dispersive spectrometer for microzone composition analysis. The results showed that a satisfied CaZrO3 sample could be obtained by in situ decomposition pore forming technology with calcium/zirconium molar ratio of 1:1.02. The CaZrO3 grains were developed better when the samples were preheated at 200°C first and then heated at 1600°C for 3 h. The apparent porosity of CaZrO3 samples were increased to 28.5%, and the thermal conductivity reduced to 1.219 W/(m·K) compared with the heavy CaZrO3 samples, which could be used as CaZrO3 refractory aggregates with the lower thermal conductivity.