Silicon and germanium present distinct and interesting transport properties. However, composites made of silicon‐germanium (SiGe) have resulted in a breakthrough in terms of their transport properties. Currently, these alloys are used in different applications, such as microelectronic devices and integrated circuits, photovoltaic cells, and thermoelectric applications. With respect to thermoelectricity, in the last decades, Si0.8Ge0.2 has attracted significant attention as an energy harvesting material, for powering space applications and other industrial applications. This chapter focuses on the recent advances and new approaches in silicon‐germanium (Si1−xGex) nanostructures for thermoelectric devices with high thermoelectric efficiency obtained through magnetron sputtering.