The deposition of Germanium (Ge) prior to the conversion of Si(100) into 3C‐SiC(100) results in changes of the structure and surface morphology of the formed silicon carbide layer. First of all it reduces the thickness of the 3C‐SiC layer grown during the conversion process and therefore the probability of voids formation. Secondly, it increases the nucleation density of the formed 3C‐SiC nuclei and therefore, decreases the grain size at Ge coverages below two monolayers. These affect the roughness of the SiC surface positively by modifying the width of the SiC‐Si interface. If the Ge coverages exceed two monolayers the structural and morphological properties begin to degrade. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)