We report the growth of chemically-bound organic overlayers on planar hydroxylated oxide surfaces, oxidized silicon and glass, using dimethyl-zinc plus alkane-thiols. Infrared spectroscopy of the layers indicates that they are similar in density and ordering to self-assembled octadecyl-trichlorosilane layers. Similar reactions can also be used to grow multilayer structures. When multilayers are grown, significant smoothing of the surface is noted. The strategies reported here lend themselves to the production of nanocomposite materials consisting of alternating layers of organic and inorganic material.