Zirconium dioxide (ZrO2) films have been grown on Si(100), Si(111), and SiO2/Si substrates heated at the range from room temperature to 800 °C by vacuum evaporation. X‐ray diffraction and reflection high‐energy electron diffraction observations reveal the epitaxial growth of tetragonal ZrO2(200) films on Si(100) substrates at 800 °C. The epitaxial imperfection is caused by preferentially oriented tetragonal ZrO2(002) grains. The crystalline system of ZrO2films depends on the substrate temperature. The crystalline perfection and the orientation of tetragonal ZrO2films grown at 800 °C depend on the substrate orientation.