Potential variations around the grain boundaries (GBs) on the surface in undoped n-BaSi2 epitaxial films on Si(111) and Si(001) were analyzed using Kelvin prove force microcopy. The potentials were higher at GBs than those in the BaSi2 grains on Si(111). The average barrier height was approximately 30 meV at the GBs, indicating that the enhanced potentials repulse photogenerated holes so that the charge carrier recombination can be effectively reduced. In contrast, the potentials were smaller at GBs in the BaSi2 on Si(001), and the average barrier heights were approximately 30 and 50 meV along Si[1–10] and [110], respectively.