The thermal oxidation of Ge-implanted Si single crystals has been investigated for different Ge doses (3×1015 cm−2 and 3×1016 cm−2) and different oxidation processes (in wet ambient at 920 °C for 30, 60, and 120 min, or dry ambient at 1100 °C for 30 min). The oxide roughness, the oxidation rate, the Ge diffusion, precipitation, and clustering, have been monitored by several experimental techniques: atomic force microscopy, transmission electron microscopy, Rutherford backscattering spectrometry, and x-ray absorption spectroscopy. We found that the surface roughness is related to the segregation of Ge at the oxide/substrate interface, occurring when the oxidation rate is faster than the Ge diffusion, in particular at the higher implanted dose (3×1016 cm−2) when processed in a wet ambient. For these conditions, we also observed an oxidation rate enhancement with respect to pure Si, and a strong indication that pure Ge clusters were formed. When a critical Ge concentration at the interface is reached, the oxidation mechanisms change and the oxidation rate is reduced, along with Ge diffusion into the substrate and a consequent reduction of the Ge fraction at the interface. Nevertheless, the oxide roughness still increases despite the Ge concentration reduction, resulting from the initial nucleation of precipitates.