The morphology and composition of porous silicon samples with thermally evaporated copper coatings were studied using atomic-force microscopy (AFM), infrared spectroscopy (IR), and X-ray photoelectron spectroscopy (XPS). Our research demonstrated that nanocomposites obtained with this method involve both metallic copper and copper oxide. The results indicate that vacuum thermal deposition of copper promotes efficient penetration of this element into the porous silicon structure and retards the oxidation process of the porous layer during long-term storage in the atmosphere.