ZnO/TiO2 nanohybrid structures have been synthesized by the simple method of the site-specific deposition of titanium oxide on ZnO nanorods. The polarity of the ZnO (0001) surface plays an important role in the formation of the nanohybrid structures. Using high-resolution transmission electron microscopy, we observed that the amorphous TiO2 particles that are connected to ZnO nanorods are 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. In addition, the size, aspect ratio, and TiO2 structures can be fully controlled in the fabrication process and subsequent annealing treatments.