For a characterization of interface and “bulk” properties of Ge films grown on Si(111) by Sb surfactant-mediated epitaxy, grazing incidence x-ray diffraction and transmission electron microscopy have been used. The interface roughness, defect structure, and strain state have been investigated in dependence of film thickness and growth temperature. For all growth parameters, atomically smooth interfaces are observed. For thin Ge layers, about 75% of the strain induced by the lattice mismatch is relaxed by misfit dislocations at the Ge/Si interface. Only a slight increase of the degree of relaxation is found for thicker films. At growth temperatures below about 600 °C, the formation of twins is observed, which can be avoided at higher temperatures.