Using high-resolution core-level photoemission measurements, we show that two different metastable species exist on a Si(111)-(7×7) surface, instead of only one as suggested in the literature. One metastable species has a finite lifetime and is composed of both molecular and atomic oxygen. The other one, which is formed by atomic oxygen only, is stable in terms of time at 300 and 100 K but disappears after annealing at 600 K. The present study reconciles the inconsistent former results and provides a detailed atomic-level understanding of the complex initial oxidation process of this surface.