Activation energies of the thermally‐activated reordering processes in high‐density, vapour deposited disordered Ge films are derived from an analysis of intensity variations in second derivative energy distribution photo‐emission spectra. The results indicate that films prepared by carefully controlled cooling to 20°C following vapour‐deposition onto heated polished silica substrates at temperatures in the range120°C ≲ Ts ≲ 140°Cundergo a sharp disordered‐crystalline transition at250 ± 20°Cwith an activation energy of1.4 ± 0.4 eVupon subsequent annealing. This behaviour, together with their d.c. conductivity and photo‐emission spectral profile characteristics, provides strong evidence for a unique continuous network ‘glassy’ state containing a minimum of unsaturated bonds.