Zn O ( 0001 ) ∕ Si ( 111 ) interface is engineered by using a three-step technique, involving low-temperature Mg deposition, oxidation, and MgO homoepitaxy. The double heterostructure of MgO(111)∕Mg(0001)∕Si(111) formed at −10°C prevents the Si surface from oxidation and serves as an excellent template for single-domain ZnO epitaxy, which is confirmed with in situ reflection high-energy electron diffraction observation and ex situ characterization by transmission electron microscopy, x-ray diffraction, and photoluminescence. The low-temperature interface engineering method can also be applied to control other reactive metal/Si interfaces and obtain high-quality oxide templates accordingly.