Most semiconductor materials such as Si, Ge, and GaAs are subject to oxidation when exposed to oxidants. This results in difficulties in the heterointegration of epitaxial oxides on these semiconductors. Even though certain oxides may be thermodynamically stable when placed in contact with semiconductors, direct epitaxy of these oxides encounters kinetic difficulties due to the loss of epitaxy caused by the formation of an amorphous oxide at the interface. In this article, we address some important issues on the heteroepitaxy of oxides on semiconductors and show a stepped growth method that utilizes the kinetic characteristics of the growth process to suppress the oxidation of the substrate surface and thereby achieve oxide films with a high degree of crystallinity. The epitaxy of high-quality SrTiO3 (STO) thin films directly on Si was achieved. The chemical and structural properties of the STO/Si interface were evaluated in situ using reflection high-energy electron diffraction, x-ray photoelectron spectroscopy, and scanning tunneling microscopy, and ex situ using transmission electron microscopy and electron energy loss spectroscopy.