A Y2O3-SiO2 nanocomposite doped with Eu3+ was obtained by a sol-gel method and characterized by X-ray diffraction, IR, 29Si NMR and laser-excited luminescence spectroscopy. It was found that small (2-3 nm) yttria nanoparticles are homogeneously dispersed in, and interacting with, the amorphous silica matrix. Luminescence spectroscopy indicates that the Eu3+ ion is preferentially located inside or at the surface of highly disordered Y2O3 nanoparticles. These luminescent nanocomposites form a class of materials which could find applications in the field of phosphors.