Abstract: The ZnO-CdS core-shell composite nanorods with CdS shell layer thicknesses of 5 and 20 nm were synthesized by combining the hydrothermal growth of ZnO nanorods with the sputtering thin-film deposition of CdS crystallites. The microstructures and optical properties of the ZnO-CdS nanorods were associated with the CdS shell layer thickness. A thicker CdS shell layer resulted in a rougher surface morphology, more crystal defects, and a broader optical absorbance edge in the ZnO-CdS rods. The ZnO-CdS (20 nm) nanorods thus engaged in more photoactivity in this study. When they were further subjected to a postannealing procedure in ambient Ar/H2, this resulted in the layer-like CdS shell layers being converted into the serrated CdS shell layers. By contrast, the ZnO-CdS nanorods conducted with the postannealing procedure exhibited superior photoactivity and photoelectrochemical performance; the substantial changes in the microstructures and optical properties of the composite nanorods following postannealing in this study might account for the observed results.