In this paper, we successfully synthesized three kinds of typical ZnO micro/nanocrystallites including flakes, columns, and pyramids by means of different facile wet chemical routes. The growth environment plays a crucial role in the morphologies of these ZnO micro/nanocrystallites. At the same time, we find that physical/chemical properties of these ZnO samples are dependent on their exposed surface, and the order of gas sensing and photocatalytic efficiency of the ZnO crystal planes is (0001) > {10 (1) over bar0} > {10 (1) over bar1} and (000 (1) over bar). On the basis of structural analyses of various exposed surfaces and related X-ray photoelectron spectroscopy, we deeply discussed the effect of definite surface structures on their gas sensing and photocatalytic properties.National Natural Science Foundation of China [20725310, 20721001, 20673085, 20801045]; National Basic Research Program of China [2007CB815303, 2009CB939804

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