Using electron beam evaporation, a Si/CeO2/Si(111) structure has been grown in a molecular beam epitaxy machine. In situ low energy electron diffraction, cross sectional transmission electron microscopy, selected area diffraction, and atomic force microscopy have been used to structurally characterize the overlying silicon layer and show it to be single crystalline and epitaxially oriented. Rutherford backscattering and energy dispersive x-ray analysis have been used to confirm the presence of a continuous 23 Å CeO2 layer at the interface. Rutherford backscattering and x-ray photoemission spectroscopy show an additional presence of cerium both at the exposed silicon surface and incorporated in low levels (~ 1%) within the silicon film, suggesting a growth mechanism with cerium riding atop the silicon growth front leaving behind small amounts of cerium incorporated in the growing silicon crystal