The combined X-ray absorption and emission spectroscopy approach was applied for the detailed electronic structure and composition studies of silicon nanoparticles produced by the ultrasound milling of highly and lowly doped Si nanowires formed by metal-assisted wet chemical etching. The ultrasoft X-ray emission spectroscopy and synchrotron based X-ray absorption near edges structure spectroscopy techniques were utilize to study the valence and conduction bands electronic structure together with developed surface phase composition qualitative analysis. Our achieved results based on the implemented surface sensitive techniques strongly suggest that nanoparticles under studies show a significant presence of the silicon suboxides depending on the pre-nature of initial Si wafers. The controlled variation of the Si nanoparticles surface composition and electronic structure, including band gap engineering, can open a new prospective for a wide range Si-based nanostructures application including the integration of such structures with organic or biological systems.