Abstract The preparation, characterization and photoluminescent study of Eu 3+ ions doped into the RE 2(WO 4) 3 matrix ( RE=La and Gd), which was produced by the Pechini method at 750°C are reported. This method is based on polyesterification between citric acid and ethylene glycol, producing a material at low temperature. The X-ray diffraction patterns of the powder materials show the characteristic lines of the rare-earth tungstates. The infrared data are compatible with a T d point group symmetry for the tungsten atom units in both compounds. The excitation spectra of these systems ( λ em=615 nm) showed an intense broad band with maximum at 265 nm related to the O→W ligand-to-metal charge-transfer state. The emission spectra of the Eu 3+ ion ( λ excitation=393 nm) presented peaks arising from the 5 D J → 7 F J′ transitions ( J=0–3 and J′=0–4) and are compatible with a C nv symmetry. The values of Ω 2 experimental intensity parameters (25.8×10 −20 and 21.5×10 −20 cm 2 for La 3+ and Gd 3+ ions, respectively), reflect the hypersensitive character of the 5 D 0→ 7 F 2 transition and indicate that the Eu 3+ ion is in a highly polarizable chemical environment, suggesting a considerable covalent character of the metal–donor atom interaction. The high emission quantum efficiencies of the RE 2(WO 4) 3:Eu 3+ materials (68% for La 3+ and 64% for Gd 3+) suggest that these systems are promising phosphors. The CIE chromaticity coordinates indicate that they are comparable to those of the commercially available red phosphor in cathode ray tubes.