This letter discusses the reaction between (001) oriented Si surfaces and photoexcited fluorine gas resulting in the removal of the native Si oxide. For an F2/Ar gas system, the bulk Si was etched in areas where the native Si oxide had been completely removed. However, by using an F2/H2gas system, only the native Si oxide was removed. We used this method to remove the native Si oxide in Si epitaxial growth. A high‐quality single‐crystal Si film surface was obtained up to a maximum temperature of 600 °C through this Si growth process. We also characterized the etching of a thermal oxide, silicon nitride, and silicon carbide.