A method for removing SiO2 and producing an ordered Si(100) surface using Sr or SrO has been developed. In this technique, a few monolayers of Sr or SrO are deposited onto the as-received Si(100) wafer in an ultrahigh vacuum molecular-beam epitaxy system. The substrate is then heated to ∼800 °C for about 5 min, the SiO2 is removed to leave behind a Sr- or SrO-terminated ordered Si(100) surface. This Sr- or SrO-terminated Si(100) surface is well suited for the growth of crystalline high-k dielectric SrTiO3 films. Temperature programmed desorption measurements were carried out to understand the mechanism of removing SiO2 from Si(100) using Sr or SrO. The species we observed coming off the surface during the temperature cycle were mainly SiO and O, no significant amount of Sr containing species was observed. We conclude that the SiO2 removal is due to the catalytic reaction SiO2+Sr(or SrO)→SiO(g)+O+Sr(or SrO). The reaction SiO2+Si→2SiO(g) at the SiO2/Si interface is limited and the pit formation is suppressed. The main roles that Sr or SrO play during the oxide removal process are catalysts promoting SiO formation and passivating the newly exposed Si surface, preventing further etching and the formation of pits in the substrate. © 2002 American Vacuum Society.