In this paper, we report the RHEED and XPS studies of the decomposition of silicon dioxide by the bombardment of metal ions and the growth of ultrathin crystalline zirconia oxide film on silicon. Through XPS analysis, it was found that silicon dioxide could be decomposed by the bombardment of Zr ions in high temperature and lower partial pressure. Silicon dioxide was decomposed into evaporated silicon oxide, while part of the oxygen in silicon dioxide reacted with metal Zr ions to form stable zirconia oxide film. The metal ions reacted with silicon dioxide homogenously. Because of the smoothness of native silicon dioxide surface and atomically abrupt silicon dioxide interface with silicon, native oxide layer on silicon wafer was evenly removed and a sharp stable crystalline zirconia oxide interface with silicon was formed. The crystalline yittria-stabilized zirconia oxide (YSZ) film with equivalent electrical oxide thickness 1.46 nm show excellent electrical properties, the interface state density less than 2 × 1011 eV -1 cm -2 and leakage current 1.1 × 10-3 A/cm 2 at 1.0 V bias. It demonstrates that this method can be used to the deposition of high-κ metal oxide as alternative dielectrics for future generation device.