The migration of oxygen vacancies (V_O) in ceria-based systems is crucial to their functionality in applications. Yet, although the V_O's structure and the distribution of the Ce³⁺ polarons at the CeO₂(111) surface has received extensive attention, the dynamic behaviors of V_O's and polarons are not fully understood. By combining density functional theory calculations and ab initio molecular dynamics simulations, we show that the movements of V_O's and polarons exhibit very distinct entanglement characteristics within a temperature range of 300–900 K, and that the positions of the Ce³⁺ polarons play a key role in the V_O migration. Long-distance vacancy migration occurs at moderate temperatures when the “suitable” Ce³⁺ distribution remains long enough to promote oxygen migration. This study provides microscopic insight into the interplay between the electronic and ionic charge transport in ceria that will be beneficial for the rational design of conductive ceria-based materials.