In this paper, two lanthanide-polyoxometalate (LnW(10)) complexes were bonded on the surface of the polyethyleneimine (PEI)-modified silica nanoparticles with different sizes, resulting in the formation of LnW(10)/PEI/SiO2 particles. The hybrid core-shell particles were characterized by infrared, luminescent spectra, scanning electronic microscope, and transmission electronic microscope. The particles obtained exhibit the fine spherical core-shell structure and the excellent luminescence properties. The luminescence spectra studies revealed that the formation of LnW(10)/PEI/SiO2 particles and the size of particle have an influence on the luminescence properties of lanthanide ions. (C) 2012 Published by Elsevier B.V.