In this paper, based on the typical SiO2-B2O3-CaO-Na2O-TiO2 borosilicate glass, the cerium-containing perovskite glass-ceramic waste form was prepared by heat treatment crystallization method. The effect of different Fe2O3 content on the phase structure and chemical stability of the waste form was studied by DSC, XRD, FTIR, SEM-EDS and ICP. The results show that with the addition of Fe2O3, the diffraction peak intensity of CeO2 crystal gradually decreases, the uniform of perovskite (CaTiO3) grain distribution shows a trend of increasing first and then decreasing, and the normalized leaching rates of all elements show a trend of decreasing first and then increasing. When the content of Fe2O3 is 6% (mass fraction), the CeO2 crystal disappears, the distribution of grains is the most uniform, and the normalized leaching rate of elements is the lowest. After 28 d, the normalized leaching rates (g·m-2·d-1) of elements in all samples are lower than the order of magnitude of 10-3, indicating that the prepared glass-ceramic waste form has excellent chemical stability. The findings of this research offer theoretical support and experimental guidance for the study of perovskite glass-ceramics solidified high-level liquid waste.