The defect behaviors, such as fundamental point defect, defect pair formation and oxygen vacancy migration in ceria, were studied on the basis of energy minimization calculations. The result shows that anion Frenkel disorder is the preferred intrinsic disorder, and it is easier to be dissolved in CeO2 for CaO and SrO than for MgO and BaO via an oxygen vacancy compensation mechanism. The association energy of an oxygen vacancy with a substitutional cation depends on dopant cation radius. The favorable migration route for oxygen vacancy with the lowest migration energy is from the second neighbor site to another one.