Abstract The role of grain boundaries on oxygen surface exchange in an oxide ion conductor is reported. Atomic‐scale characterization of the microstructure and chemical composition near the grain boundaries of gadolinia‐doped ceria (GDC) thin films show the segregation of dopants and oxygen vacancies along the grain boundaries using the energy dispersive spectroscopy in scanning transmission electron microscopy (STEM‐EDS). Kelvin probe microscopy is employed to verify the charge distribution near grain boundaries and shows that the grain boundary is positively charged, indicating a high concentration of oxygen vacancies. AC impedance spectroscopy on polycrystalline GDC membranes with thin interfacial layers with different grain boundary densities at the cathodes demonstrated that the cells with higher grain boundary density result in lower electrode impedance and higher exchange current density. These experimental evidences clearly show that grain boundaries on the surface provide preferential reaction sites for facilitated oxygen incorporation into the GDC electrolyte.