Modulation of grain boundary barrier in ZnO layer by polar liquid, was investigated in ZnMgO/ZnO heterostructures grown by plasma-assisted molecular beam epitaxy. Traditionally, surface adsorbates can only affect the surface atoms or surface electronic states. However, it was found that the electronic conduction property of ZnO far from the surface could be tailored obviously by the polar liquid adsorbed on the ZnMgO surface. Physically, this phenomenon is supposed to be caused by the electrostatical couple between the liquid polarity and the grain boundary barrier in the ZnO layer through crystal polarization field.