Nanostructured Zinc Oxide (ZnO) was deposited on silicon (c-Si) and macroporous silicon (m-PS) using a radio frequency (RF) reactive magnetron sputtering technique. Two RF powers of 60 and 80 W were selected for ZnO deposition on the substrates. Furthermore, the c-Si and m-PS substrate temperatures were kept at 500 and 800 °C, respectively. The morphological, structural, and optical characteristics of the samples were studied using scanning electron microscopy (SEM), an X-ray diffractometer (XRD), X-ray photoelectron spectroscopy (XPS), and photoluminescence spectroscopy (PL). The SEM images revealed the formation of ZnO nanorods on the c-Si and ZnO nanostructures constituted by the assembly of nanorods. It has been found that the increasing RF sputtering power caused the rise in the residual stress. In addition, the increase in the deposition temperature caused an improvement in the arrangement of the crystals, which was attributed to the decrease in crystal defects.