Elemental diffusion in ceramics can modulate the conductivity as well as fuel cell performance. Here, we report the effect of diffusion on NiO coated samarium doped ceria (SDC) with temperature and correlated with conductivity. NiO thin film was deposited using electron beam physical vapor deposition over the pre-sintered SDC substrate and subsequently treated at 800 degrees C, 1000 degrees C, and 1200 degrees C. Depth profiling analysis across NiO-SDC hetero-interface using FESEM-EDAX revealed that the width of the diffusion zone increased with temperature. All the constituent ions like Ni, Sm and Ce diffuse mutually without forming any impurity phases at the NiO-SDC interface. The estimated diffusivity values demonstrated that the nickel predominantly diffuses through the grain boundary of SDC. The constituent cations were found to diffuse several hundred nanometers through grain boundaries at a temperature of 1200 degrees C. An increase in the electrical conductivity was observed in proportion to the width of the diffusion layer. The diffusion of nickel predominantly along the grain boundary reduced the grain boundary resistance by altering the space charge potential at the NiO-SDC interface. Our study demonstrates that the modification of grain boundary through the controlled diffusion of metal ions reduce the resistance for oxygen ion transport in NiO-SDC electrolyte.