Employed for a long time in optical disks, Ge2Sb2Te5 is nowadays considered the most promising material also for phase-change nonvolatile memories. In the current paper, Ge–Sb–Te phase-change material thin films with a nominal composition of Ge2Sb2Te5 were grown by molecular beam epitaxy on slightly mismatched GaSb and InAs substrates with (001) and (111) orientations. In situ quadrupole mass spectrometry and reflection high-energy electron diffraction allowed tight control of the growth parameters, revealing that Ge2Sb2Te5 grows in epitaxial fashion only within a narrow window of substrate temperatures around 200 °C. Smooth surfaces were achieved solely on (111)-oriented substrates. Rough surfaces and interfaces were observed by transmission electron microscopy for films grown on (001)-oriented substrates. Whereas films deposited on (001) substrates possess two different vertical epitaxial …