The role of the first atomic layers in epitaxial relationship and interface characteristics of SrTiO3 films on CeO2/yttria-stabilized zirconia (YSZ)/Si(001) substrates was investigated. Although SrTiO3 film deposited on CeO2/YSZ/Si directly was preferentially (110)-oriented, epitaxial SrTiO3(001) films could be grown on CeO2/YSZ/Si by controlling first atomic layer of the films. In the case of SrTiO3 film starting from TiO2 layer, the neither ion drift nor charge injection occurred in the SrTiO3/CeO2 interface. On the other hand, for the film starting from SrO layer, an injection-type hysteresis was observed. This is probably due to the electron traps in the interface.