Monolayer and multilayer films of trichlorogermane hexyl propylate (Ge6) were formed by the self-assembly method on hydroxylated silicon substrates. The results showed that this kind of trichlorogermane had virtually the same self-assembly behavior as trichlorosilanes. Ellipsometry proved that the self-assembled monolayers and multilayers (SAMs) of Ge6 exhibited a tilted orientation to the substrate surface. The multilayer film of Ge6 on silicon substrate was obtained by reducing the monolayer SAMs to alcohol hydroxylated surface with LiAlH4 and repeating the self-assembly process. The self-assembled multilayer film was calcined in air at 500 degrees C to form a thin layer of GeO2 on SiO2/Si substrate surface. The XPS measurement detected the formation of GeO2 layer.