The process of effective solar energy harvesting and conversion requires efficient photon absorption, followed by charge generation and separation, then electron transfer. Nanostructured materials have been considered as potential building blocks for the development of future generations of solar cells. Much attention has been given to wide-bandgap semiconductor nanowires, combined and sensitized with low-bandgap semiconductors effectively attached to the nanowires for low-cost and highly efficient solar cells. Here, the in situ growth of lead sulfide (PbS) nanoparticles on the surface of zinc oxide (ZnO) nanowires grown by the Successive Ionic Layer Adsorption and Reaction (SILAR) technique is presented for different numbers of cycles. The morphology and structure of PbS nanoparticles are confirmed by Scanning Electron Microscopy (SEM), revealing the decoration of the nanowires with the PbS nanoparticles, Transmission Electron Microscopy (TEM) and HR-TEM, showing the tight attachment of PbS nanoparticles on the surface of the ZnO nanowires. The Selected Area Electron Diffraction (SAED) confirms the crystallization of the PbS. Photoluminescence spectra show a broad and more intense deep-level emission band.