We report on a controlled synthesis of two novel semiconducting heterostructures: heterocrystalline-ZnS/single-crystalline-ZnO biaxial nanobelts and side-to-side single-crystalline ZnS/ZnO biaxial nanobelts via a simple one-step thermal evaporation method. In the first heterostructure, a ZnS domain is composed of the heterocrystalline superlattice (3C-ZnS) N /(2H-ZnS) M [111]-[0001] with the atomically smooth interface between wurtzite and zinc blende ZnS fragments. High-spatial resolution cathodoluminescence studies on individual heterostructures for the first time reveal a new ultraviolet emission peak ( approximately 355 nm), which is not observed in separate ZnS or ZnO nanostructures. The present hererostructures are expected to become valuable not only with respect to fundamental research but also for a design of new broad-range ultraviolet nanoscale lasers and sensors.