The hydration resistance of CaO materials prepared by Ca(OH)₂ calcination with chelating compounds are investigated in this paper. The crystalline phases and microstructure characteristics of sintered specimens were studied by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy and energy dispersive spectrometer (SEM, EDS). The bulk density, apparent porosity, and hydration resistance of samples were also tested. The results showed that chelating compounds improved the hydration resistance of the treated CaO specimens significantly. The surface-pretreated specimens showed an increase in bulk density and a decrease in apparent porosity after heating. The surface pretreatment of the Ti chelating compound promoted the solid phase sintering and grain growth of CaO specimens, which increased the density of the heated CaO sample. The Al chelating compound promoted the liquid-phase sintering of CaO specimens, which led to the grain growth and increased density of the sample. CaO grains were bonded by the formed tricalcium aluminate (C₃A) and the apparent porosity of the sample was reduced, reducing the contact area of CaO with water vapor. The Al chelating compound was more effective in improving the hydration resistance of the CaO material in the situation of this study.