A rare earth doped form of ceria (CeO2) is of interest as a potential candidate for solid oxide fuel cells (SOFCs) because of its relatively high oxygen ion conductivity at temperatures below 600 °C. At the present time, computational chemistry has reached a certain maturity which allows the prediction of materials properties that are difficult to observe experimentally. However, understanding of the roles of dopants in the oxygen ion conduction in CeO2 is still incomplete for quantitatively reliable analysis due to the strong electron correlation of 4f electrons. In this study, density functional theory calculations with Hubbard U corrections are used to discuss ionic/covalent interactions in rare-earth-doped CeO2 and their consequences to oxygen ion conduction. This study suggests that the variable occupancy of empty 4f orbitals is important typically for early Ln elements to produce the covalent interactions that essentially affect the formation and migration of oxygen vacancies. This finding is important in understanding the factors responsible for oxygen ion diffusion in doped CeO2.