The BiMeVOx family of compounds appears to be more attractive for applications at low temperatures when ionic conductivity is the determining parameter. The objective of this study was to analysis the influence of voltage of the behavior of the Schottky barrier in both BiCuVOX and BiTiVOX. The samples were analyzed by atomic force microscopy and electric force microscopy (EFM). EFM experiments were conducted to map the electric field distribution on the surface. The formation of Schottky barriers was observed, and their height and width measured. BiCuVOX samples show a barrier width of 140 nm, and BiTiVOX shows a barrier width of 350 nm. The applied voltage has no effect on the barrier width but increases the peak height as observed in the cantilever frequency as measured with the EFM technique.