In this paper, an investigation of the properties of Cu and Cu/MgO nanoparticles (NPs) is presented. The NPs were obtained with gas-phase synthesis, and the MgO shells or matrices were formed via the co-deposition method on inert substrates. SEM and AFM were used to investigate the NP morphology on Si/SiOx, quartz, and HOPG. The Cu NPs revealed flattening of their shape, and when they were deposited on HOPG, diffusion and formation of small chains were observed. The embedding of Cu NPs in MgO was confirmed by TEM and EDX maps. XPS showed that Cu was in its metallic state, regardless of the presence of the surrounding MgO. UV–Vis revealed the presence of an intense localized surface plasmon resonance (LSPR) for Cu/MgO and for “bare” NPs. These results confirmed the role of MgO as a protective transparent medium for Cu, and the wavelength position of the LSPR in the Cu/MgO system was consistent with calculations. The wavelength position of the LSPR observed for “bare” and post-oxidized Cu NPs was probably affected by the formation of copper oxide shells after exposure to air. This study paves the way for the use of Cu/MgO NPs as plasmonic nanomaterials in applications such as photovoltaics and sensor technology.