The role of Pr doping on double Schottky barrier formations at ZnO single grain boundaries was investigated by the combination of current-voltage measurements, atomic-resolution Z-contrast scanning transmission electron microscopy, and first-principles calculations. Although Pr segregated to the specific atomic site along the boundaries, it was found not to be the direct cause of nonlinear current-voltage properties. Instead, under appropriate annealing conditions, Pr enhances formations of acceptor-type native defects that are essential for the creation of double Schottky barriers in ZnO.