In this study, we deposit a Ge-rich Ge–Sb–Te alloy by physical vapor deposition (PVD) in the amorphous phase on silicon substrates. We study in-situ, by X-ray and ultraviolet photoemission spectroscopies (XPS and UPS), the electronic properties and carefully ascertain the alloy composition to be GST 29 20 28. Subsequently, Raman spectroscopy is employed to corroborate the results from the photoemission study. X-ray diffraction is used upon annealing to study the crystallization of such an alloy and identify the effects of phase separation and segregation of crystalline Ge with the formation of grains along the [111] direction, as expected for such Ge-rich Ge–Sb–Te alloys. In addition, we report on the electrical characterization of single memory cells containing the Ge-rich Ge–Sb–Te alloy, including IV characteristic curves, programming curves, and SET and RESET operation performance, as well as upon annealing temperature. A fair alignment of the electrical parameters with the current state-of-the-art of conventional (GeTe) n-(Sb 2 Te 3) m alloys, deposited by PVD, is found, but with enhanced thermal stability, which allows for data retention up to 230 C.