An investigation was made on the electronic structure of 4d transition metal layered oxide material of Li₂RuO₃ using X-ray photoelectron spectroscopy (XPS) and X-ray absorption spectroscopy (XAS). The intensity of O [Formula: see text] pre-edge peak increased for Li ion extracted samples, suggesting increased ligand holes. The Ru 3d XPS spectrum suggested the variation of local structure around Ru ions by extraction of Li ions. We conclude that the delithiation from Li₂RuO₃ is charge compensated by O anions, and that the creation of the ligand holes reorganizes electronic structures composed of highly hybridized Ru 4d and O 2p orbitals.