Cerium carbonates are important precursors for the production of CeO2, which have a decisive effect on the properties of CeO2. The crystal characteristics of cerium carbonate compounds depend on the control of supersaturating in reactive crystallization, and the solubility of cerium carbonate compounds in the NaCl-H2O system are important basic data. In this work, cerium carbonates were synthesized by homogeneous precipitation method at the temperature range of 298.15~363.15 K. The generated solids were characterized by X-ray diffractometer (XRD), scanning electron microscope (SEM) and thermogravimetric analyzer (TG). The results showed that Ce2(CO3)3?8H2O was obtained below 323.15 K and transferred to CeCO3OH above 343.15 K. The solubility of the two cerium carbonate compounds in the NaCl-H2O system were determined by the classical isothermal method. The results showed that the solubility of Ce2(CO3)3?8H2O increased with the increase of temperature and concentration of NaCl, while the solubility of CeCO3OH increased with the increase of concentration of NaCl, and decreased with the increase of temperature. The solubility of Ce2(CO3)3?8H2O in water at 298.15 K was 4.08×10-6 mol/kg, which was of the same order of magnitude as the solubility of cerium carbonate [Ce2(CO3)3] that was 2.17×10-7~2.17×10-6 mol/kg at 298.15 K. The results indicated the reliability of the experimental data measured in this work. A thermodynamic model for predicting the solubility of Ce2(CO3)3?8H2O and CeCO3OH in the NaCl-H2O system was finally established by using the ELEC-NRTL equation embedded in the Aspen Plus platform. The solubility products of Ce2(CO3)3?8H2O and CeCO3OH were obtained by regression of their solubility data in water on the basis of an infinite dilution assumption. The species such as CeCO3+, CeOH2+, CeHCO32+ were introduced into the thermodynamic model on basis of the speciation method and their equilibrium constants were calculated by Van't Hoff isothermal formula. The new ion pair parameters of Ce3+-HCO3- and Ce3+-Cl- were obtained by regression of the experimental data to improve the predictive ability of the new model. The predicted values of the established thermodynamic model were well in agreement with the experimental data.