Oxygen ion conductivity of doped ceria is observed to be two-three orders of magnitude higher than yttria stabilized zirconia, the most widely used solid electrolyte material at temperatures below 600 °C. Gadolinium doped ceria (GDC) is known to be one of the most promising solid electrolyte materials for operation of solid oxide fuel cells below 600 °C. To understand the atomic defect migration in GDC, we have used total energy calculations within the framework of density functional theory to follow oxygen vacancy migration in GDC. We report activation energies for various oxygen vacancy migration pathways in GDC. Oxygen vacancy formation and migration were evaluated for first, second, and third nearest neighbor positions to a Gd³⁺ ion. Due to the comparable ionic radii of Gd³⁺ and host Ce⁴⁺ ions, the first nearest neighbor site with respect to the dopant cation is found to be the most favorable oxygen vacancy formation site. The migration pathway where the vacancy migrates from a second to first nearest neighbor is found to be most favorable. The calculated activation energies for oxygen vacancy migration in GDC are compared against the reported measured and calculated values from the literature. This work will provide a foundation for the development of a kinetic lattice Monte Carlo model for vacancy diffusion in GDC, which will improve the understanding of oxygen ion conductivity in doped ceria.