We demonstrate remarkably rapid oxidation of (100) silicon at room temperature catalyzed by the presence of Cu3Si. Thermal oxidation of Si is normally carried out at temperatures above 700 °C. Oxidation of many metal silicides occurs more rapidly than that of Si, but under controlled conditions results in a surface layer of SiO2. In contrast, the oxidation process described here produces a thick layer of SiO2underneath the copper‐rich surface layer. The SiO2layer grows spontaneously to over 1 &mgr;m in thickness in several weeks in air at room temperature. Analysis by Rutherford backscattering, Auger electron spectroscopy, cross‐sectional transmission electron microscopy, and scanning electron microscopy reveals the presence of Cu3Si at the buried SiO2/Si interface, epitaxially related to the underlying Si substrate. Catalytic action by this silicide phase appears responsible for the unusual oxidation process.