We report that twin-free single-crystalline Pd nanowire (NW) arrays grow epitaxially in a selected pattern on a substrate. Parallel aligned Pd NWs are synthesized on a SrTiO(3) (110) substrate in a very high density. On a SrTiO(3) (001) substrate, Pd NWs grow horizontally in two perpendicular directions. Vertical Pd NWs are synthesized instead of horizontal NWs when a c-cut sapphire substrate is employed. We reveal that the atomic structure of the substrate surface determines the geometry and orientation of seeds, which in turn direct the growth patterns of the NWs. The interface energy between the NW material and the substrate is also critical in determining the NW growth pattern. Polarization-dependent localized surface plasmon resonance of as-synthesized epitaxial Pd NW arrays is investigated for application as a plasmonic platform.