A novel nanostructure of a side-to-side SnO2/ZnO/SnO2 triaxial nanobelt has been achieved via a simple oxidation of theseparated Zn and Sn powders. Each nanobelt has a broad inner ribbon of ZnO with two symmetric SnO2 sides, and all of the belts are singlecrystal. This composite structure demonstrates the possibility of selective growth based on the polar surface and also suggests that heterogeneousgrowth can proceed on both polar surfaces of ZnO ±(0001). The corresponding room-temperature photoluminescence has also been tailoredand been discussed in this paper. Our approach presented here would be helpful in designing and preparing many other heterostructures tomeet the growing demands of nanoscale science and technology.