The transfer energy of oxygen vacancy of La and Y co-doped CeO 2 is investigated in which the total amount of La and Y is fixed at 20 at%. Although both the La 3+ (1.16 Å) and Y 3+ (1.032 Å) ions are larger than the Ce 4+ ions (0.97 Å), individual single doping of La and Y results in an increase and a decrease in the CeO 2 lattice constant, respectively, due to the effect of the critical ionic radius ( r c ). As the La/Y ratio varies, the lattice constant increases as the La content increases, which leads to a decrease in the migration energy of the oxygen vacancy in the grain interior. When La and Y are co-doped at a ratio of 2:18, its lattice constant is almost the same as that of pure CeO 2 in which the dissociation energy of the oxygen vacancy achieves the lowest value due to the minimum lattice-strain energy. The migration energy at the grain boundary also decreases with increasing La content. This result is explained by the degree of grain boundary segregation of the dopant.