Well-aligned ZnO/Zn(S,O) heterostructure nanorods have been synthesized through a well-designed chemical vapor deposition synthesis process. The as-synthesized ZnO/Zn(S,O) heterostructures exhibit a single crystal characteristic and a transitive interface with obvious composition gradient. X-ray Energy dispersive spectrometer (EDS) analysis demonstrates that ZnS-phase is rich in the nanorod bottom during the initial nucleation process and the S element content has a drastic decrease along the heterostructure nanorod from the bottom to the top, while O element is spatially detected in the whole rod. Room-temperature cathodoluminescence measurements verify two UV emissions at 330 nm and 385 nm for respective Zn(S,O) and ZnO phases with a strong defect-related emission band in visible range. Finally, the growth mechanism and optical emissions of ZnO/Zn(S,O) heterostructure nanorods are discussed.