In this study, we present a full characterization of the electronic properties of phase change material (PCM) double-layered heterostructures deposited on silicon substrates. Thin films of amorphous Ge-rich Ge-Sb-Te (GGST) alloys were grown by physical vapor deposition on Sb2Te3 and on Ge2Sb2Te5 layers. The two heterostructures were characterized in situ by X-ray and ultraviolet photoemission spectroscopies (XPS and UPS) during the formation of the interface between the first and the second layer (top GGST film). The evolution of the composition across the heterostructure interface and information on interdiffusion were obtained. We found that, for both cases, the final composition of the GGST layer was close to Ge2SbTe2 (GST212), which is a thermodynamically favorable off-stoichiometry GeSbTe alloy in the Sb-GeTe pseudobinary of the ternary phase diagram. Density functional theory calculations allowed us to calculate the density of states for the valence band of the amorphous phase of GST212, which was in good agreement with the experimental valence bands measured in situ by UPS. The same heterostructures were characterized by X-ray diffraction as a function of the annealing temperature. Differences in the crystallization process are discussed on the basis of the photoemission results.