The nanostructured particles of europium(III) complexes with tri-n-octyl phosphineoxide (TOPO) and naphthoyl trifluoroacetone (NTA) ligands containing gold nanoparticles (GNPs) were successfully prepared by using the modified Stöber method. Their morphologies and optical properties were investigated. The results show that they are stable in aqueous solution. The TEM image indicates that the average diameter of nanoparticles of europium(III) complexes containing GNPs is about 115 nm. Monosize nanospheres containing GNPs of 18 nm were produced. The nanostructured luminescent complexes of europium(III) integrated with plasmon structure of GNPs exhibit efficient luminescence properties.