Germanium films, which were obliquely deposited in relatively high pressures of oxygen, were studied with TEM and ESCA. TEM photomicrographs of the films show that large elongated clusters appear as the pressure of oxygen during film deposition increases. The number of these clusters increases as the deposition angle (the angle between the source flux and the substrate plane) decreases. ESCA results indicate that the films consist primarily of Ge and HCl‐soluble GeO2. The amount of oxygen uptake in the films increases as the pressure of oxygen during deposition increases and∕or as the deposition angle decreases. These results are important to the understanding of the anomalous photovoltaic effect.