Rare earth phosphosilicates (Li 1Ψx Eu x ) 1/6 Pb 1/3 Zr 2 (PO 4 ) 17/6 (SiO 4 ) 1/6 04x41 have been synthesized via a sol+gel route. The powder X-ray di4raction has been analyzed with the Nasicontype structure. The Rietveld analysis of the structure performed in space group R3 shows a statistical distribution of ions La 3Ψ , Eu 3Ψ , and Pb 2Ψ over the positions 3a (occupation 10%) and 3b (occupation 90%) of the so-called M1 site. In agreement with these results, the Eu 3Ψ luminescence analysis in these phases exhibits two sites for Eu 3Ψ , both are noncentrosymmetric, revealing a local disorder in the compounds, which is also supported by the inhomogeneous broadening of the emission lines. The luminescence characteristics of this family of silicates have been investigated for various x values. Under excitation at 254 nm, the distinct emissions of Pb 2Ψ and of Eu 3Ψ are observed. The excitation of Eu 3Ψ ions occurs directly via the charge transfer state or after Pb 2Ψ PEu 3Ψ energy transfer. Concentration quenching of the Eu 3Ψ emission is also investigated.