We studied the surface characterization of milled–silicon nitride nano-powders by XPS and TEM. The change of the chemical state and morphology of the oxide layer on the surface of Si3N4 nano-particles before and after a conventional wet–ball–milling process are investigated by X–ray photoelectron spectroscopy for measuring the chemical state of the oxide layer and transmission electron microscopy for observing surface morphology. The native oxide layers of as-received Si3N4 powders confirmed by HREM observation and their chemical states were different each other. As increasing ball–milling time, the chemical composition and the volume of oxide layer in Si3N4 powders were changed. The chemical state of as–received Si3N4 powder was near to SiO2 phase. After ball–milling process for long time, that of the milled Si3N4 powder shifted to Si2N2O phase. As increasing ball-milling time, the oxide layer of Si3N4 powder was also increased.