In this paper, vertically aligned (VA) liquid crystal (LC) modes were investigated using the alkyl chain ordering effect of self-assembled monolayers (SAMs) prepared on the anisotropic inorganic surface. On the anisotropic surface prepared through oblique ion beam irradiations, the SAM molecules are adsorbed, producing macroscopic alkyl chain ordering, which can determine the pretilt direction of the vertically aligned LC molecules through the intermolecular interactions on the surface.