The heterostructures obtained by growing a-Ge on a-Si:H and a-Si have been investigated by synchrotron radiation photoemission. We measured valence band and core level spectra on the heterostructures grown in situ under ultrahigh-vacuum conditions. A step-by-step monitoring of possible band-bending changes during the interface formation enabled us to determine unambiguously the band discontinuities. The measured values of the valence band discontinuity were 0.2 ± 0.1 eV for a-Si:H/a-Ge and 0.0 ± 0.1 eV for a-Si/a-Ge, respectively. Evidence was found for the formation of abrupt interfaces without interdiffusion.