We report the formation processes of interface dangling bonds (Pb centers) during initial oxidation of a clean Si(111) surface using an ultrahigh-vacuum electron-spin-resonance technique. At the oxidation of one or two Si layer(s), the Pb center density reached around 2.5-3.0 x 10(12) cm(-2), which is the same density as in the case of thick SiO2. This result shows that the Pb center density does not originate from the long-range accumulation of the structural stress between two materials, but from the chemical reactions of oxidation within a few Si atomic layers.