Multilayer structures based on semiconductor materials are being actively studied for their use in various solar energy detectors and converters. Due to the combination of properties of individual materials, an overall improvement of performance characteristics can be achieved in their multilayer design. In the present work, a technique for the preparation of layered structures based on PbS on the surface of silicon substrates has been tested for the first time. The principal possibility of chemical deposition of lead sulfide films from aqueous media at 80 °C by varying the initial state of the silicon substrate and the presence of the sensitive NH4Cl addition is presented. The morphology, elemental and phase composition, structural, and optical characteristics of the obtained lead sulfide films were studied by ICP, SEM-EDX, XRD and Raman spectroscopy. The photoelectrochemical effect of initial silicon substrates and layered PbS/Si structures was obtained using a solar simulator.