ZnO nanowire–CdO composite nanostructures were fabricated by a simple two-step process involving ammonia solution method and thermal evaporation. First, ZnO nanowires (NWs) were grown on Si substrate by aqueous ammonia solution method and then CdO was deposited on these ZnO NWs by thermal evaporation of cadmium chloride powder. The surface morphology and structure of the synthesized composite structures were analyzed by scanning electron microscopy, X-ray diffraction and transmission electron microscopy. The optical absorbance spectrum showed that ZnO NW–CdO composites can absorb light up to 550 nm. The photoluminescence spectrum of the composite structure does not show any CdO-related emission peak and also there was no band gap modification of ZnO due to CdO. The photocurrent measurements showed that ZnO NW–CdO composite structures have better photocurrent when compared with the bare ZnO NWs