Si 2p core-level spectroscopy is a unique tool to determine the chemical composition and spatial extension of the suboxide layer present at the Si/SiO2 interface. In the case of ultra-thin oxide films (thickness <10 Å), the high surface sensitivity provided by the tunability of synchrotron radiation allows the observation of four energetically well-separated oxidation states, generally attributed to a silicon atom with an increasing number of oxygen first neighbors, and hence often denoted Sin+(with n=1,…,4). After a brief review of two decades of XPS studies on the Si/SiO2 interface, we give an account of the recent debate concerning the possible contribution of the second oxygen neighbor shell to the chemical shift, which, if effective, would modify the picture of the interface. Then, we examine the benefit derived from the use of very high energy resolution (70 meV at hv=130 eV), and we try to determine, for this system, what are the limits of this spectroscopy. To illustrate the latter point, among various case studies (thermal oxides, room temperature adsorption etc.), we treat in more detail the case of the H-terminated Si(1 11) surface oxidized by atomic oxygen, and discuss our data in the light of previous XPS and vibrational spectroscopy studies.