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Flower-like ZnO nanorod and hexagonal ZnO nanoplate were prepared via hydrothermal process. The relationship between exposed surfaces of ZnO nanostructures and their optical properties was explored. It was demonstrated that the visible emission originated from defects on the surfaces dependent on their crystal planes. Hexagonal ZnO nanoplates which enclosed by positive surface of (0001) Zn2+ plane and negative surface of (000) O2- plane exhibited high emission intensity in violet, blue and green regions resulted from Zn interstitials and oxygen vacancies. Meanwhile, flower-like ZnO nanostructures with enclosed nonpolar of {1001} prismatic plane and high energy polar of {1011} pyramidal planes at the tip of rod exhibited high emission intensity of Zn interstitials and oxygen vacancies after annealing.