AbstractIn this paper, we demonstrate a simple method to synthesize ZnO/TiO₂ nanohybrid structure arrays based on the site-specific deposition of titanium oxide on ZnO nanorods under the hydrothermal condition. We have found that the polarity of the ZnO (0001) surface plays an important role in the formation of the nanohybrid structures. Each ZnO nanorod is assembled with one TiO₂ particle only at the (0001) end surface. High-resolution transmission electron microscopy study shows that the TiO₂ particles that are connected to ZnO nanorods are amorphous. By annealing at different temperatures, these particles can be transformed to nanocrystals of the anatase and rutile phases, which have a particular relationship with the orientation of ZnO nanorods and good interface structures. This work provides a rational approach to the assembly of complex nanohybrids using the intrinsic properties of ZnO nanocrystals.