We have observed that in the low‐temperature deposition of thin films of SiO2onto semiconductor surfaces by remote plasma enhanced chemical vapor deposition, oxidation occurs at the semiconductor–SiO2interface. Thissubcutaneousprocess generates a thin film ofnativeoxide, which can then play a significant role in determining the electrical properties of the semiconductor/oxide interface. The native oxide formed on Si is SiO2, and we have determined that the growth of this oxide does not interfere with the formation of device quality interfaces provided that the thickness of the deposited oxide layer is less than ∼250 Å. For an oxide thickness greater than ∼250–300 Å, trapping states associated with defects produced along with the subcutaneous oxidation degrade the properties of the Si/SiO2interface. The native oxide that forms on Ge surfaces during SiO2depositions is the water‐soluble, rutile‐structured form of GeO2, and the presence of this oxide significantly degrades the electrical quality of the Ge/dielectric interface. In the case of the compound semiconductor interfaces with deposited SiO2, native oxide formation also generally degrades the electrical characteristics. For example, the oxide that forms on GaAs is predominantly Ga2O3, whereas the oxide on CdTe displays both Cd–O and Te–O bonding. Interposing a thin layer of epitaxial, and pseudomorphic Si between a Ge, GaAs, or CdTe semiconductor surface and the deposited SiO2film, can provide a viable approach to the formation of good metal–oxide‐semiconductor (MOS) devices, provided that the subcutaneous oxidation of the Si layer that occurs during oxide deposition does not ‘‘punchthrough’’ that layer and thereby allow for the oxidation of the underlying Ge, GaAs, or CdTe substrate as well.