In-plane growth of Mg2SiO4 nanowires on Si substrates is achieved by using a vapor transport method with Au nanoparticles as catalyst. The self-assembly of the as-grown nanowires shows dependence on the substrate orientation, i.e., they are along one, two, and three particular directions on Si (110), (100), and (111) substrates, respectively. Detailed electron microscopy studies suggest that the Si substrates participate in the formation of Mg2SiO4, and the epitaxial growth of the nanowires is confined along the Si < 110 > directions. This synthesis route is quite reliable, and the dimensions of the Mg2SiO4 nanowires can be well controlled by the experiment parameters. Furthermore, using these nanowires, a lithography-free method is demonstrated to fabricate nanowalls on Si substrates by controlled chemical etching. The Au nanoparticle catalyzed in-plane epitaxial growth of the Mg2SiO4 nanowires hinges on the intimate interactions between substrates, nanoparticles, and nanowires, and our study may help to advance the developments of novel nanomaterials and functional nanodevices.