Due to their interesting optical and electronic properties, silicon nanocrystals (Si NCs) are the subject of intense research activity. The definition of their electronic structure is not trivial, neither from a theoretical nor from an experimental point of view. In fact, the models and methodologies developed for bulk materials cannot be directly applied to study these nanostructures where size-related effects, like quantum confinement (QC) and surface related phenomena, play a major role. In this work, X-ray Photoelectron Spectroscopy (XPS) was used to study the electronic structure of Si NCs embedded in SiO2. The energy differences among Si0+ 2s and Si0+ 2p core levels and the valence band maximum (VBM) were monitored. XPS data were combined with a direct measurement of the energy band gap by photoluminescence analysis, providing a complete picture of the electronic structure of Si NCs as a function of their …