In the present study, the heterostructures of ZnO Nanoparticle (NP)/CdS nanowire (NW), SnO2NP/CdS NW, NiS NP/CdS NW, FeS NP/CdS NW, Ag2S NP/CdS NW, and Au NP/CdS NW have been successfully fabricated via the two-stage solvothermal process. Field-emission scan electron microscopy (FESEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS) ... [Show full abstract] were adopted to characterize the as-prepared products. The optical properties of the as-obtained heterostructures were separately investigated. New insights into understanding and controlling the synthesis of different NW heterostructures are demonstrated in the reliable solvothermal route. We demonstrate that CdS NWs synthesized for 2h are the bifunctional mediator acting as catalyst or active spot for the growth of NW heterostructures Furthermore, understanding and controlling this phenomenon is a great asset for the realization of the formation mechanism of the NW heterostructures and opens up new ways toward for construction of other semiconductor heterostructures with novel properties.