Since environmental pollution has exceeded the limit of natural purification, [1] semiconductor-based photocatalytic reactions have attracted intense interest as an effective way of purifying air and water contaminants. [2] Among the various semiconductors, zinc oxide, with a direct wide bandgap (DE = 3.37 eV), is of special importance for the photocatalytic generation of hydrogen peroxide, [3] which can be utilized for the degradation of organic pollutants and the sterilization of bacteria and viruses. [2,4] Due to the fact that a photocatalytic reaction occurs at the interface between catalyst surfaces and organic pollutants, [2] it is highly feasible that the photocatalytic activity of ZnO is strongly dependent on the growth direction of the crystal plane. Such speculation gives us the impetus to explore the relationship between surface orientation of ZnO crystals and their photocatalytic efficiency. However, due to an intrinsic anisotropy in the growth rate v of ZnO,, hexagonal rods elongated along the c-axis have been predominantly synthesized. [5,6] Such an anisotropic tendency in crystal growth makes it difficult to directly probe the relationship between face orientation and photocatalytic activity. Here we report the novel face-tunable synthesis of nano-and microscale ZnO crystals with different ratios of polar to nonpolar faces. With these morphology-controlled crystals, we were able to clearly demonstrate a strong dependence of photocatalytic activity on a specific crystal plane.In Figure 1, we show schematic models for face-tunable synthetic routes to ZnO crystals. The morphologies of the resulting ZnO crystals were investigated with field-emission scanning electron microscopy (FESEM), as shown in Figure 2, and the theoretical surface areas of four different samples, estimated from the FESEM results, are summarized in Table 1.First, hexagonal ZnO nanorods were prepared simply by hydrothermal treatment of dip-coated ZnO nanoparticles on a Si wafer with a uniform size of 4 nm (Fig. 1a).[6a] The corresponding FESEM image of Figure 2a reveals the formation of a dense array of ZnO nanorods with a uniform diameter of 100 nm and a length of 1.5 lm. Due to a one-dimensional nanostructure extended along the [0001] direction, the ZnO nanorods have a larger population of nonpolar {011 0} faces than polar {0001} ones. In order to suppress crystal growth along the [0001] axis, we tried to protect the Zn 2+ -terminated (0001) plane, that is, Zn (0001), through complexation between Zn 2+ ions and citrate ligands. [7] On the basis of this strategy, hexagonal nanoplates with a uniform diameter of 1.0 lm and a thickness of 50 nm were successfully obtained, as can be seen clearly from the FESEM image in Figure 2b. Such formation of nanoplates with a high proportion of polar {0001} planes is surely due to a strong suppression of crystal growth along the [0001] axis with a relative enhancement of crystal growth along the [011 0] direction, as illustrated in Figure 1b. Similarly, the tailored synthesis of diverse ZnO na...