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La2O3: Eu(3+) nanoparticles were prepared by Gly assistant combustion synthesis with the sizes from 12-28 nm, and a characterization of XRD was done. Spectral properties of the nanoparticles were compared with the bulk. High resolution spectra were measured. Site selective excitation was employed to probe the local environments of Eu(3+) ions in La2O3 nanoparticles. The luminescent centers on the surface and the center of the nanoparticles were excited respectively. The spectra were related to surface information. The luminescence from C3v site and the site with lower symmetry on the surface was distinguished.