We have investigated the preparation conditions of single-oriented (002) Zr film on n-(001) Si by varying the sputtering parameters during deposition using an ultrahigh-vacuum dc magnetron sputtering system. The crystallinity and preferential orientational plane of Zr film on Si were examined by X-ray diffraction analysis, and the chemical nature at the Zr/Si interface was evaluated by X-ray photoelectron spectroscopy and Auger electron spectroscopy analyses. We found that the Zr film with the single-oriented (002) plane grew on (001) Si under the conditions of sputtering power above 50 W and substrate temperature range of 350–400°C. For this reason, it is speculated that a thin interdiffusion layer, which consists of elementary atoms (Zr and Si) and Zr silicide, formed at the Si interface plays the role of a buffer layer to relax the misfit between Zr and Si.